Ion exchangeable glass, glass ceramics and methods for making the same

ABSTRACT

Glass-ceramics and precursor glasses that are crystallizable to glass-ceramics are disclosed. The glass-ceramics of one or more embodiments include rutile, anatase, armalcolite or a combination thereof as the predominant crystalline phase. Such glasses and glass-ceramics may include compositions of, in mole %: SiO2 in the range from about 45 to about 75; Al2O3 in the range from about 4 to about 25; P2O5 in the range from about 0 to about 10; MgO in the range from about 0 to about 8; R2O in the range from about 0 to about 33; ZnO in the range from about 0 to about 8; ZrO2 in the range from about 0 to about 4; B2O3 in the range from about 0 to about 12, and one or more nucleating agents in the range from about 0.5 to about 12. In some glass-ceramic articles, the total crystalline phase includes up to 20% by weight of the glass-ceramic article.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 14/469,688 filed on Aug. 27, 2014, the content of which is relied upon and incorporated herein by reference in its entirety, and claims the benefit of priority under 35 U.S.C. § 120 of U.S. Provisional Application Ser. No. 62/018,737, filed on Jun. 30, 2014, and of U.S. Provisional Application Ser. No. 61/871,986, filed on Aug. 30, 2013, the contents of which are relied upon and incorporated herein by reference in their entirety.

BACKGROUND

The disclosure relates to glass-ceramics and precursor glasses that are crystallizable to glass-ceramics, which may each or both be strengthened by ion exchange processes; methods for making the same and articles including the same. In particular, this disclosure relates to translucent or opaque glass-ceramics that include a total crystalline phase up to about 20% by weight and crystal phases such as anatase, rutile, armalcolite, or a combination thereof, and the precursor glasses used to form such glass-ceramics.

In the past decade, electronic devices such as notebook computers, personal digital assistants, portable navigation device, media players, mobile phones, portable inventory devices and other such devices (frequently referred to as “portable computing devices”) have converged, while at the same time becoming small, light, and functionally more powerful. One factor contributing to the development and availability of such smaller devices is an ability to increase computational density and operating speed by ever decreasing electronic component sizes. However, the trend to smaller, lighter, and functionally more powerful electronic devices presents a continuing challenge regarding design of some components of the portable computing devices.

Components associated with portable computing devices encountering particular design challenges include the enclosure or housing used to house the various internal/electronic components. This design challenge generally arises from two conflicting design goals—the desirability of making the enclosure or housing lighter and thinner, and the desirability of making the enclosure or housing stronger and more rigid. Lighter enclosures or housings, typically thin plastic structures with few fasteners, tend to be more flexible while having a tendency to buckle and bow as opposed to stronger and more rigid enclosures or housings, typically thicker plastic structures with more fasteners having more weight. Unfortunately, the increased weight of the stronger, more rigid plastic structures might lead to user dissatisfaction, while the bowing and buckling of the lighter structures might damage the internal/electronic components of the portable computing devices, which almost certainly can lead to user dissatisfaction. Furthermore, plastics are easily scratched due to their low hardness, so their appearance degrades with use.

Among known classes of materials are glass-ceramics that are used widely in various other applications. For example, glass-ceramics are used widely in kitchens as cooktops, cookware, and eating utensils, such as bowls, dinner plates, and the like. Transparent glass-ceramics are used in the production of oven and/or furnace windows, optical elements, mirror substrates, and the like. Glass-ceramics are typically made by crystallizing precursor glasses, which are formulated to be crystallizable, at specified temperatures for specified periods of time to nucleate and grow crystalline phases in a glass matrix.

In some instances, it is desirable to form glass-ceramic articles for use in portable computing devices having specific optical properties, such as opacity and color. Known glass-ceramics based on the SiO₂—Al₂O₃—Li₂O glass system include those having either β-quartz solid solution (“β-quartz ss” or “β-quartz”) as the predominant crystalline phase or β-spodumene solid solution (“β-spodumene ss” or “β-spodumene”) as the predominant crystalline phase. Such known glass-ceramics can require specific heat treatment conditions to achieve a desirable color and exhibit lower strength, which may be due to the size and shape of the crystals, their stress filed in the glass and the strength of the residual glass. In addition, such glass ceramics may also exhibit an undesirable level of brittleness, which may be due to a high concentration of crystalline phase(s). Furthermore such glass-ceramics tend to have liquidus viscosities that preclude the use of high throughput forming methods such as float, slot draw, or fusion draw. For example, known glass-ceramics are formed from precursor glasses having liquidus viscosities of about 10 kP, which are not suitable for fusion draw, where liquidus viscosities of above 100 kP or above 200 kP are generally required. Accordingly, although glass-ceramics exhibit desirable properties such as high opacity, various degrees of translucency, and surface luster, which are generally not achievable by fusion forming, such glass-ceramics cannot take advantage of the pristine surfaces and thinness (e.g., 2 mm or less) achieved by fusion forming process.

In view of the foregoing problems with existing enclosures or housings, there exists a need for glass-ceramic and precursor glass materials that are ion exchangeable and with high liquidus viscosities (i.e. liquidus viscosities that enable forming methods such as slot draw, fusion draw, and the like), which provide improved enclosures or housings for portable computing devices, in a potentially more cost effective manner. Also, there exists a need for such materials that provide improved color properties (e.g., whiteness levels) and/or other opaque colors while addressing in an aesthetically pleasing manner the design challenges of creating lightweight, strong, and rigid enclosures or housings.

SUMMARY

One or more aspects of this disclosure pertain to glass-ceramics or glass-ceramic articles with a predominant crystalline phase including anatase, rutile, armalcolite or a combination thereof. In one or more embodiments, the glass-ceramic articles disclosed herein include a total crystalline phase including up to 20% by volume of the glass-ceramic articles. In some embodiments, the glass-ceramic articles include a predominant crystalline phase comprising anatase, rutile, armalcolite or a combination thereof. In one or more embodiments, the predominant crystalline phase comprises crystals having a minor dimension of about 1000 nm or less (e.g., about 500 nm or less or about 100 nm or less). The at least a portion of the crystals in the predominant phase may have a major dimension and an aspect ratio of the major dimension to the minor dimension of about 2 or greater. In some instances, the aspect ratio may be about 5 or greater. In one or more embodiments, the total crystalline phase may be about 20 wt. % or less, about 12 wt. % or less, or about 5 wt. % or less of the glass-ceramic article. In specific instances, the total crystalline phase may include armalcolite and the total crystalline phase may comprise 5 wt. % of the glass-ceramic article.

The glass-ceramics described herein may be characterized by the processes by which they can be formed. Such glass-ceramics may be formed by float processes, fusion processes, slot draw process, thin rolling processes, or a combination thereof. In some embodiments, the glass-ceramic may be shaped into or have a three-dimensional shape. In one or more embodiments, the properties of the precursor glass composition and glass may determine this processing flexibility. The glass-ceramic may exhibit a liquidus viscosity of about 10 kilopoise (kP) or greater, about 20 kP or greater, about 50 kP or greater, or about 100 kP or greater.

In one or more embodiments, the glass-ceramics (and/or the precursor glass composition and/or glasses including such compositions) include, in mol %, SiO₂ in the range from about 45 to about 75, Al₂O₃ in the range from about 4 to about 25, P₂O₅ in the range from about 0 to about 10 (or from about 0.1 to about 10), MgO in the range from about 0 to about 8, R₂O in the range from about 0 to about 33, ZnO in the range from about 0 to about 8, ZrO₂ in the range from about 0 to about 4, B₂O₃ in the range from about 0 to about 12, and one or more nucleating agents in the range from about 0.5 to about 12. In one variant, the nucleating agent may include TiO₂. In another variant, the composition exhibits the compositional relationship (R₂O—Al₂O₃) is in the range from about −4 to about 4. In one or more embodiments, R₂O may include one or more of Na₂O, Li₂O and K₂O. In one or more specific embodiments, the composition includes, in mol %, Li₂O in the range from about 0 to about 12, Na₂O in the range from about 4 to about 20 and/or K₂O in the range from about 0 to about 2. In an even more specific embodiment, the composition may optionally include a non-zero amount of SnO₂ up to about 2 mol %, and/or B₂O₃ in the range from about 2 mol % to about 10 mol %.

The glass-ceramic articles according to one or more embodiments may include a compressive stress layer (“CS layer”) extending from a surface of the glass-ceramic article to a depth in the glass-ceramic article. The CS layer may be formed by an ion exchange process. As used herein, the term “ion exchanged” or “IX” is understood to mean glass-ceramics (and/or glasses) disclosed herein that are chemically strengthened by ion exchange processes in which the glass-ceramics (and/or glasses) are treated with a heated salt bath containing ions having a different ionic radius than ions that are present in the glass-ceramic (and/or glass) surface and/or bulk. The ions in the bath replace those ions in the glass-ceramic (and/or glass), which may be smaller in radius (or vice versa depending on the temperature conditions). Glass-ceramics and glasses that are subjected to such ion exchange treatment(s) may be referred to herein as “ion exchanged (IX) glass-ceramics”, or “ion exchanged (IX) glasses”. In one variant, the CS layer has a compressive stress of at least about 200 MPa. The depth of the CS layer (“DOL”) may be at least about 15 μm. The glass-ceramic articles disclosed herein may exhibit a Vickers indentation crack initiation load of at least 10 kgf.

In one variant, the glass-ceramic articles described herein exhibit a color presented in CIELAB color space coordinates determined from specular reflectance measurements using a spectrophotometer with various illuminants. In one example, as measured using a spectrophotometer with illuminant D65, the glass-ceramic articles exhibit CIELAB color space coordinates of: CIE a* in the range from about −2 to about 8; CIE b* in the range from about −7 to about 30; and CIE L* in the range from about 85 to about 100. In another example, as measured using a spectrophotometer with illuminant F02, the glass-ceramic articles exhibit CIELAB color space coordinates of: CIE a* in the range from about −1 to about 0; CIE b* in the range from about −8 to about −3; and CIE L* in the range from about 80 to about 100. These color coordinates may be exhibited when specular reflectance is included or excluded in the measurement.

A second aspect of the instant disclosure pertains to glass precursors of the glass-ceramic articles described herein. In one or more embodiments, the glass precursors may be aluminosilicate glass precursors, which may be characterized as including a fusion formable composition. In one or more embodiments, the glass precursor composition that exhibits a liquidus viscosity of about 10 kilopoise (kP) or greater, about 20 kP or greater, about 50 kP or greater, or about 100 kP or greater. In one variant, the glass precursor composition may exhibit a liquidus temperature of less than about 1400° C. or less than about 1200° C. or less than about 1100° C. The glass-ceramic articles may exhibit these liquidus viscosity or liquidus temperature values when evaluated using know methods in the art.

A third aspect of the instant disclosure pertains to a method of making a glass-ceramic article having predominant crystalline phase including anatase, rutile, armalcolite or a combination thereof. In one or more embodiments, the method includes melting a batch for, and forming, a glass article having a composition that includes SiO₂ in the range from about 45 to about 75, Al₂O₃ in the range from about 4 to about 25, P₂O₅ in the range from about 0 to about 10, MgO in the range from about 0.01 to about 8, R₂O in the range from about 0 to about 33, ZnO in the range from about 0 to about 8, ZrO₂ in the range from about 0 to about 4, B₂O₃ in the range from about 0 to about 12, and one or more nucleating agents in the range from about 0.5 to about 12. The formed glass article may exhibit a liquidus viscosity of about 10 kP or greater or about 20 kP or greater and a liquidus temperature of less than about 1400° C. in the formation of the glass article. In one or more embodiments, the method may further include ceramming the glass article at a temperature between about 50° C. greater than an annealing temperature of the glass article and about 1100° C. for a period of time to cause the generation of a glass-ceramic article which includes a predominant crystalline phase comprising anatase, rutile, armalcolite or a combination thereof and, thereafter, cooling the glass-ceramic article to room temperature.

In one option, the method may include forming a CS layer in the glass article and/or glass-ceramic article having a compressive stress of about 200 MPa or greater. In some embodiments, the CS layer extends from a surface of the glass article and/or glass-ceramic into the glass article and/or glass-ceramic at a DOL of about 15 μm or greater. The CS layer may be formed by an ion exchange treatment.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

Any ranges of values set forth in this specification contemplate all values within the range and are to be construed as support for claims reciting any sub-ranges having endpoints which are real number values within the specified range in question. By way of a hypothetical illustrative example, a recitation in this disclosure of a range of from about 1 to 5 shall be considered to support claims to any of the following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and 4-5. In addition, it is to be understood that such terms as “is,” “are,” “includes,” “having,” “comprises,” and the like are words of convenience and are not to be construed as limiting terms and yet may encompass the terms “comprises,” “consists essentially of,” “consists of,” and the like as is appropriate.

These and other aspects, advantages, and salient features of this disclosure will become apparent from the following description, the accompanying drawings and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between fracture toughness and the amount of TiO₂, according to one or more embodiments;

FIG. 2 shows a XRD pattern for glass-ceramics formed from Examples 3-5;

FIG. 3 shows a scanning electron microscope (SEM) backscattered electron image (BEI) micrograph of a glass-ceramics formed from Example 3;

FIG. 4 shows a SEM micrograph (BEI) of a glass-ceramic formed from Example 4;

FIG. 5 shows a SEM micrograph (BEI) of one of a glass-ceramic formed from Example 5;

FIG. 6 shows a XRD pattern for a glass-ceramic formed from Example 44;

FIG. 7 shows a SEM micrograph (BEI) of the glass-ceramic shown in FIG. 6;

FIG. 8 shows a XRD pattern for glass-ceramics formed from Examples 63-68;

FIG. 9 shows a transmission spectra of glass-ceramics formed from Examples 63-68, and having a thickness of about 1.0 mm;

FIG. 10 is a graph comparing the transmission spectra of glass-ceramics formed from Example 94 and having a thickness of about 0.8 mm, after various heat treatments;

FIG. 11 shows a graph illustrating the relationship between TiO₂ content, liquidus viscosity and liquidus temperature, based on selected Examples from Table 1;

FIG. 12 shows a graph illustrating the variations in CIELAB color coordinates as a function of the compositional relationship (R₂O—Al₂O₃), based on selected Examples from Table 1;

FIG. 13 is a graph illustrating the total transmittance of glass-ceramics formed from Examples 63 and 65-68;

FIG. 14 is a graph illustrating the opacity of the glass-ceramics shown in FIG. 1;

FIG. 15 is a graph showing the x-ray diffraction spectra of the crystalline phase of the glass-ceramics formed from Examples 130-132;

FIGS. 16A and 16B show high angle annular dark field (HAADF) mapping images for a glass-ceramic of Example 131;

FIGS. 17A-17D show energy-dispersive x-ray (EDX) mapping images for a glass-ceramic formed from Example 131 for elements Mg, Ti, Al and Si, respectively;

FIG. 18A is a graph of CIELAB color space coordinates a* and b* for glass-ceramics formed from Examples 130-132 and Comparative Example 135;

FIG. 18B is a graph of CIELAB color space coordinate L* for glass-ceramics formed from Examples 130-132 and Comparative Example 135;

FIG. 19 is a graph showing the concentration of K⁺ ions present in a glass-ceramic formed from Example 131 (after ceramming at 920° C. for 4 hours) as a function of depth, after being ion exchanged in a molten salt bath including KNO₃, having a temperature of 430° C., for two different time periods: 8 hours and 16 hours;

FIG. 20 is a graph showing the concentration of Na⁺ ions present in the glass-ceramic formed from Example 131 (after ceramming at 920° C. for 4 hours) as a function of depth, after being ion exchanged in a molten salt bath including NaNO₃, having a temperature of 430° C., for two different time periods: 8 hours and 16 hours.

DETAILED DESCRIPTION

In the following description of exemplary aspects and/or embodiments of this disclosure, reference is made to the accompanying drawings that form a part hereof, and in which are shown by way of illustration specific aspects and/or embodiments in which this disclosure may be practiced. While these aspects and/or embodiments are described in sufficient detail to enable those skilled in the art to practice this disclosure, it will nevertheless be understood that no limitation of the scope of this disclosure is thereby intended. Alterations and further modifications of the features illustrated herein, and additional applications of the principles illustrated herein, which would occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of this disclosure.

As noted, various aspects and/or embodiments of this disclosure relate to an article including a glass ceramic that may be characterized as translucent and/or opaque. In some embodiments, the glass-ceramic may have a white color, although other colors are contemplated. The glass-ceramic materials may include crystalline phases of anatase, rutile, armalcolite, or a combination thereof and may be ion exchangeable.

The glass-ceramics described herein may be used in a variety of electronic devices or portable computing devices, light diffusers, automotive, appliances, and even architectural applications. To that end, it is desirable that precursor glasses thereto are formulated to have a sufficiently low softening point and/or a sufficiently low coefficient of thermal expansion so as to be compatible with manipulation into complex shapes. Accordingly, the precursor glasses used to form the glass-ceramics are also of interest and are described herein in more detail.

According to one or more aspects of this disclosure, the glass-ceramics include anatase, rutile, armalcolite or a combination thereof as the predominant crystalline phase. The glass-ceramics (and/or precursor glass compositions and/or glass that includes such a composition) of one or more embodiments may include, in mol %, SiO₂ in the range from about 45 to about 75; Al₂O₃ in the range from about 4 to about 25; P₂O₅ in the range from about 0 to about 10; MgO in the range from about 0 to about 8; R₂O in the range from about 0 to about 33; ZnO in the range from about 0 to about 8; ZrO₂ in the range from about 0 to about 4; B₂O₃ in the range from about 0 to about 12, and one or more nucleating agents in the range from about 0.5 to about 12. The glass-ceramic (and/or precursor glass compositions and/or glass that includes such a composition) may be essentially free of As₂O₃ and Sb₂O₃. As used herein, the term “essentially free of As₂O₃ and Sb₂O₃” means that the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) comprises less than about 0.1% by weight of either of As₂O₃ or Sb₂O₃. As will be described in greater detail, the viscosity and indentation crack initiation load performance of the glass or glass-ceramic are influenced by precursor glass compositions.

In one or more embodiments, SiO₂ may be present in glass-ceramic articles (and/or precursor glass compositions and/or glass that includes such a composition) described herein, in mol %, in the range from about 45 to about 75, from about 46 to about 75, from about 47 to about 75, from about 48 to about 75, from about 49 to about 75, from about 50 to about 75, from about 51 to about 75, from about 52 to about 75, from about 53 to about 75, from about 54 to about 75, from about 55 to about 75, from about 56 to about 75, from about 57 to about 75, from about 58 to about 75, from about 59 to about 75, from about 60 to about 75, from about 62 to about 75, from about 45 to about 74, from about 45 to about 73, from about 45 to about 72, from about 45 to about 71, from about 45 to about 70, from about 45 to about 69, from about 45 to about 68, from about 45 to about 67, from about 45 to about 66, from about 45 to about 65, from about 45 to about 64, from about 45 to about 63, from about 45 to about 62, from about 45 to about 61, from about 45 to about 60, from about 46 to about 70, from about 47 to about 68, from about 48 to about 66, from about 49 to about 64, from about 50 to about 62, from about 55 to about 65, from about 51 to about 64, from about 52 to about 63, from about 53 to about 62, from about 54 to about 62, from about 55 to about 61, from about 54 to about 60, from about 62 to about 70, from about 62 to about 69, from about 62 to about 68, and all ranges and sub-ranges therebetween.

In one or more specific embodiments, SiO₂ may be present in an amount to serve as the primary glass-forming oxide or to provide a glass or glass-ceramic with sufficient chemical durability for the application for which the glass or glass-ceramic is utilized. For example, the glass or glass-ceramic may be utilized in touch module applications and may be modified to include enough SiO₂ to exhibit the requisite chemical durability for such applications, as well as to increase the viscosity for forming operations. The content of SiO₂ may be limited to control the melting temperature of the precursor glass composition. In some instances, an excess amount of SiO₂ (including, e.g., a precursor glass composition with only SiO₂) could drive the fining temperature, at 200 poise, beyond that attainable in typical glass melters so that bubbles cannot be efficiently removed from the glass or glass-ceramic formed from such precursor glass compositions. Thus the SiO₂ content should be maintained in the range from about 45 mol % to about 75 mol %, to balance manufacturing needs with good durability. In some embodiments, the precursor glass compositions with the highest liquidus viscosities that ceram to opaque, white glass-ceramics typically include SiO₂ in an amount in the range from about 50 mol % to about 65 mol %. As used herein the terms “ceram” and “heat treat” are used interchangeably and the terms “ceramming” and “heat treating” are used interchangeably and include the thermal treatment of precursor glasses to form glass-ceramics.

In one or more embodiments, Al₂O₃ may be present in the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) described herein, in mol %, in the range from about 4 to about 25, from about 5 to about 25, from about 6 to about 25, from about 7 to about 25, from about 8 to about 20, from about 9 to about 25, from about 10 to about 25, from about 11 to about 25, from about 12 to about 25, from about 4 to about 24, from about 4 to about 22, from about 4 to about 20, from about 4 to about 18, from about 4 to about 16, from about 4 to about 14, from about 4 to about 13, from about 4 to about 12, from about 5 to about 25, from about 6 to about 24, from about 7 to about 22, from about 8 to about 20, from about 9 to about 18, from about 10 to about 16, from about 10 to about 14, from about 11 to about 13, from about 12 to about 18, from about 12 to about 17, from about 12 to about 16, from about 12 to about 15, or from about 13 to about 15, and all ranges and sub-ranges therebetween. The amount of Al₂O₃ may be adjusted to serve as a glass forming oxide and/or to control the viscosity of molten precursor glass compositions.

In one or more embodiments, an increase in the amount of Al₂O₃ in a precursor glass composition relative to other alkalis and/or alkaline earths can improve or increase the durability of a glass or glass-ceramic. Without being bound by theory, it is believed that when the concentration of alkali oxide (R₂O) in a glass composition is equal to or greater than the concentration of Al₂O₃, the aluminum ions are found in tetrahedral coordination with the alkali ions acting as charge-balancers. This tetrahedral coordination greatly enhances ion exchange of glass and/or glass-ceramics formed from such precursor glass compositions. This is demonstrated in some of the Examples listed in Table I herein. In the other Examples listed in Table I, the concentration of alkali oxide is less than the concentration of aluminum ions; in this case, the divalent cation oxides (RO) can also charge balance tetrahedral aluminum to various extents. While elements such as calcium, zinc, strontium, and barium behave equivalently to two alkali ions, the high field strength of magnesium ions causes them to not fully charge balance aluminum in tetrahedral coordination, resulting in the formation of five- and six-fold coordinated aluminum. Generally, Al₂O₃ can play an important role in IXable glass and glass-ceramics since it enables a strong network backbone (i.e., high strain point) while allowing for the relatively fast diffusivity of alkali ions. Charge balanced glasses also have higher viscosity than heavily modified or per-aluminous glasses, so the Al₂O₃ content can be useful for managing the viscosity. However, when the concentration of Al₂O₃ is too high, the glass composition may exhibit a higher liquidus temperature and hence lower liquidus viscosity so the Al₂O₃ concentration of some embodiments should be in the range from about 4 mol % to about 25 mol %. Furthermore, the excess modifiers or the difference (R₂O—Al₂O₃) has a large impact on tetravalent oxide solubility. When the excess modifiers are low, there is a low solubility for tetravalent cations like TiO₂, ZrO₂, and SnO₂. This makes it easy to precipitate crystalline TiO₂ (anatase and rutile), but also raises the liquidus temperature. Thus the difference (R₂O—Al₂O₃) of some embodiments should be in the range from about −4 mol % to about 4 mol % to achieve white glass-ceramics with reasonable liquidus viscosity. To achieve embodiments that include white glass-ceramics with a liquidus viscosity greater than 50 kP, the difference (R₂O—Al₂O₃) may be in the range from about −2 mol % to about 2 mol %. Accordingly, in some embodiments, the amount of Al₂O₃ may be in the range from about 12 mol % to about 17 mol %.

In one or more embodiments, the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein include alkali oxides (R₂O) (e.g., Li₂O, Na₂O, K₂O, Rb₂O, and/or Cs₂O) that are present, in mol %, in an amount in the range from about 0 to about 40, from about 0 to about 33, from about 0 to about 20, from about 8 to about 20, or from about 12 to about 18. In one or more specific embodiments, alkali oxides (R₂O) may be present, in mol %, in an amount in the range from about 0.01 to about 40, from about 0.1 to about 40, from about 1 to about 40, from about 2 to about 40, from about 3 to about 40, from about 4 to about 40, from about 5, to about 40, from about 6 to about 40, from about 7 to about 40, from about 8 to about 40, from about 9 to about 40, from about 11 to about 40, from about 12 to about 40, from about 0.01 to about 39, from about 0.01 to about 38, from about 0.01 to about 37, from about 0.01 to about 36, from about 0.01 to about 35, from about 0.01 to about 34, from about 0.01 to about 33, from about 0.01 to about 32, from about 0.01 to about 31, from about 0.01 to about 30, from about 0.01 to about 29, from about 0.01 to about 28, from about 0.01 to about 27, from about 0.01 to about 26, from about 0.01 to about 25, from about 0.01 to about 33, from about 0.1 to about 33, from about 1 to about 33, from about 2 to about 33, from about 3 to about 33, from about 4 to about 33 from about 5 to about 33, from about 6 to about 33, from about 7 to about 33, from about 8 to about 33, from about 9 to about 33, from about 10 to about 33, from about 11 to about 33, from about 12 to about 33, from about 0.01 to about 20, from about 0.1 to about 20, from about 1 to about 20, from about 2 to about 20, from about 3 to about 20, from about 4 to about 20, from about 5 to about 20, from about 6 to about 20, from about 7 to 20, from about 8 to about 20, from about 9 to about 20, from about 10 to about 20, from about 10 to about 17, from about 11 to about 20, from about 12 to about 20, from about 1 to about 19, from about 1 to about 18, from about to 1 to about 17, from about 1 to about 16, from about 1 to about 15, from about 1 to about 14, from about 1 to about 13, from about 1 to about 12, from about 1 to about 19, from about 2 to about 18, from about 3 to about 17, from about 4 to about 16, from about 5 to about 15, from about 6 to about 14, from about 7 to about 13, from about 8 to about 12, or from about 9 to about 11, and all ranges and sub-ranges therebetween.

In one or more embodiments, the amount of alkali oxides (R₂O) may be adjusted to provide glass compositions exhibiting low melting temperature and/or low liquidus temperatures. Without being bound by theory, the addition of alkali oxide(s) may increase the coefficient of thermal expansion (CTE) and/or lower the chemical durability of the glasses and/or glass-ceramics that include such precursor glass compositions. In some cases these attributes may be altered dramatically by the addition of alkali oxide(s). The amount of excess alkali in a glass composition can also determine the ceramming or heat treatment temperature used to form the glass-ceramics and the resulting opacity of the glass-ceramics. In one or more embodiments, the inclusion of a small excess of alkali in a glass composition beyond that to charge compensate the Al₂O₃, (i.e., 0<R₂O—Al₂O₃≤1) can enhance the desirable white color in glass-ceramics that include such precursor glass compositions and can provide a precursor glass composition that exhibits a low liquidus temperature and high liquidus viscosity. Moreover, in some embodiments, to perform ion exchange, the presence of a small amount of alkali oxide (such as Li₂O and Na₂O) in the article to be exchanged may facilitate ion exchange with larger alkali ions (e.g., K⁺) (e.g., exchanging smaller alkali ions from the glass article with larger alkali ions from a molten salt bath containing such larger alkali ions). Three types of ion exchange can generally be carried out: a Na⁺ for —Li⁺ exchange, a K⁺-for-Li⁺ exchange, and/or a K⁺-for-Na⁺ exchange. A sufficiently high concentration of the small alkali oxide in the precursor glass compositions may be useful to produce a large compressive stress in the glass and/or glass-ceramics that include such glass precursor compositions, since compressive stress is proportional to the number of alkali ions that are exchanged out of the glass and/or glass-ceramic.

In a specific embodiment, Na₂O may be present, in mol %, in the range from about 4 to about 20, from about 5 to about 20, from about 6 to about 20, from about 7 to 20, from about 8 to about 20, from about 9 to about 20, from about 10 to about 20, from about 11 to about 20, from about 12 to about 20, from about 4 to about 19, from about 4 to about 18, from about to 4 to about 17, from about 4 to about 16, from about 4 to about 15, from about 4 to about 14, from about 4 to about 13, from about 4 to about 12, from about 4 to about 19, from about 5 to about 18, from about 6 to about 17, from about 7 to about 17, from about 8 to about 17, from about 9 to about 17, from about 12 to about 14, from about 10 to about 13, or from about 11 to about 12, and all ranges and sub-ranges therebetween. Na₂O is also important for controlling the liquidus temperature and viscosity as well as ion exchange and TiO₂ solubility as discussed herein. Thus, in some embodiments, the amount of Na₂O is in the range from about 4 mol % to about 20 mol % to achieve ion exchangeable white glass-ceramics, and in some embodiments, in the range from about 8 mol % to about 17 mol % to obtain liquidus viscosities above 100 kP.

In another specific embodiment, K₂O may be present, in mol %, in the range from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 5, from about 0.1 to about 4, from about 0.1 to about 3, from about 0.1 to about 2, from about 0.1 to about 1, from about 1 to about 5, from about 1 to about 4, from about 1 to about 3, from about 1 to about 2, and all ranges and sub-ranges therebetween. In one or more embodiments, the K₂O controls the CTE, refractive index, and ion exchange rate of the precursor glass and glass-ceramic. Increasing the K₂O concentration at the expense of the concentration of Na₂O increases the rate of ion exchange at the expense of compressive stress in the precursor glass and glass-ceramic, when a K⁺ for Na⁺ ion exchange is utilized. Thus the highest compressive stress values are achieved in the precursor glasses and/or glass-ceramics when the precursor glass composition includes Na₂O and no K₂O, so there are more Na⁺ ions to exchange for with K⁺ ions. However, deeper or greater DOL values for a fixed ion exchange time will be achieved in precursor glasses and glass-ceramics when up to half of the Na₂O in the precursor glass composition is replaced with K₂O. At very high K₂O amounts, the formation of leucite during the creaming process increases the liquidus temperature and lowers the liquidus viscosity, so the K₂O content of some embodiments is limited to less than 8 mol % to prevent such an increase in liquidus temperature and decrease in liquidus viscosity. In some embodiments, the K₂O content is limited to less than about 2 mol % to achieve high compressive stress.

In one or more embodiments, Li₂O may be present, in mol %, in an amount in the range from about 0 to about 15, from about 0 to about 12, from about 0 to about 10, from about 0 to about 5, from about 0 to about 2, from about 0.1 to about 15, from about 0.1 to about 12, from about 0.1 to about 10, from about 0.1 to about 5, from about 1 to about 15, from about 1 to about 10, from about 1 to about 5, or from about 1 to about 2, and all ranges and sub-ranges therebetween. In one or more embodiments, Li₂O may be used as a primary alkali during IX process. At high Li₂O contents, the formation of spodumene or lithium disilicate crystals increases the liquidus temperature, so in some embodiments, the Li₂O content is less than about 12 mol % to maintain a low liquidus temperature. Since Li⁺ ions in the precursor glass and/or glass-ceramic quickly poison K⁺ containing ion exchange baths, in embodiments utilizing such baths to exchange K⁺ ions into the precursor glass and/or glass-ceramic, the Li₂O content of the precursor glass composition is less than 2 mol %.

In one or more embodiments, the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) may exhibit the following compositional criteria: the sum Li₂O+Na₂O+K₂O may be, in mol %, in the range from about 4 to about 30, from about 4 to about 28, from about 4 to about 26, from about 4 to about 24, from about 4 to about 22, from about 4 to about 20, from about 4 to about 18, from about 4 to about 16, from about 4 to about 14, from about 4 to about 12, from about 4 to about 10, from about 6 to about 30, from about 8 to about 30, from about 10 to about 30, from about 12 to about 30, from about 14 to about 30, from about 16 to about 30, from about 16 to about 30, from about 18 to about 30, or from about 20 to about 30, and all ranges and sub-ranges therebetween.

In some embodiments, the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) described herein, exhibit the following compositional criteria: the difference (R₂O—Al₂O₃) may be, in mol %, in the range from about −4 to about 4, in the range from about −3 to about 3, from about −2 to about 2, from about −0.5 to about 2, from about −1 to about 1, from about 0 to about 1, and from about −1 to about 0, and all ranges and sub-ranges therebetween. In one or more embodiments the lower limit of the difference (R₂O—Al₂O₃) may include −4.0, −3.5, −3.0, −2.5, −2.0, −1.5, −1.0, −0.5, −0.4, −0.3, −0.2, −0.1 and all ranges and sub-ranges therebetween. In one or more embodiments the upper limit of the difference (R₂O—Al₂O₃) may include 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.4, 0.3, 0.2, 0.1 and all ranges and sub-ranges therebetween.

In one or more embodiments, the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) described herein include a nucleating agent that may be characterized as self-nucleating. As used herein, nucleating agent refers to a component in the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) that serves as the starting point of the nuclei itself (i.e., is a discontinuity or defect in the homogenous or amorphous phase from which the crystal phase is generated), and does not require other components to promote nucleation. In one or more embodiments, the nucleating agent(s) may be present, in mol %, in the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) described herein in the range from about 0.1 to about 12, from about 0.1 to about 10, from about 0.1 to about 7, from about 1 to about 5, from about bout 2 to about 4. In one or more embodiments, the nucleating agent may be present, in mol %, in the range from about 0.1 to about 10, from about 0.5 to about 10, from about 1 to about 10, from about 1 to about 12, from about 1.5 to about 10, from about 2 to about 10, from about 2.5 to about 10, from about 3 to about 10, from about 0.1 to about 7, from about 0.5 to about 7, from about 1 to about 7 from about 1.5 to about 7, from about 2 to about 7, from about 2.5 to about 7, from about 3 to about 7, from about 0.1 to about 6.5, from about 0.1 to about 6, from about 0.1 to about 5.5, from about 0.1 to about 5, from about 2 to about 5, from about 0.1 to about 4.5, from about 0.1 to about 4, from about 0.5 to about 4, from about 1 to about 4, from about 1.5 to about 4, or from about 2 to about 4, and all ranges and sub-ranges therebetween.

In one or more embodiments, the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) include TiO₂, which may be present in the form of rutile and/or anatase (after heat treatment of a glass to form a glass-ceramic). In one or more embodiments, TiO₂ is utilized and is “self-nucleating” as it does not require secondary nucleating agents to grow anatase and rutile crystals. Both rutile and anatase both have very high refractive index, for example, 2.609 and 2.488, respectively, which results in very efficient light scattering when embedded in a glass with low refractive index (e.g., around 1.5). Anatase and rutile are also birefringent and often grow in elongated grains with high aspect ratio which further adds to their scattering power, resulting in glass-ceramics with a dense opal appearance at relatively low crystal contents. As used herein, the term “dense opal” refers to a material that is not transparent, or can appear opaque to the naked eye. Materials characterized as dense opal may appear, when evaluated using some optical equipment, depending on thickness, as not completely opaque but rather translucent because there is some transparency (i.e., some light passes through the material). This dense opal appearance can be achieved in thin cross-sections (i.e., having a thickness of about 1 mm) by including less than about 12 mol % of the crystallizing component (e.g., TiO₂). Where TiO₂ is utilized, higher TiO₂ levels (e.g., >4 mole %) provide very opaque glass-ceramics at thicknesses of about 1 mm, while around 3 mole % TiO₂ provides opaque glass-ceramics at the same thickness. When TiO₂ is below 3 mole %, the liquidus viscosity of the precursor glass composition can be very high, but the opacity of the resulting glass-ceramic begins to suffer, resulting in translucent glass-ceramics. Moreover, if the concentration of TiO₂ is too low (<1.5 mol %), the precursor glass does not crystallize. Thus the TiO₂ content of some embodiments is in the range from about 1 mol % to about 12 mol %, and some embodiments include from about 2 mol % to about 5 mol %, from about 2 mol % to about 4.5 mol % TiO₂ or from about 2 mol % to about 4 mol %, to provide an desirable opacity and liquidus viscosity. In some embodiments, the glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) includes about 2 mol % of TiO₂ or more to generate an armalcolite phase. In some embodiments, the amount of TiO₂ may be about 3 mol % or greater

In one or more specific embodiments, the nucleating agent may include ZnO, ZrO₂, titanium, platinum, gold, rhodium, and other nucleating agents known in the art. In one or more embodiments, nucleating agent, and in particular, ZrO₂ may be present, in mol %, in the range from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 4, from about 0.1 to about 3, from about 0.1 to about 2, from about 0.1 to about 1, from about 1 to about 4, from about 1 to about 3, from about 1 to about 2, and all ranges and sub-ranges therebetween. Precious metals such as platinum, gold, rhodium, silver, and iridium are typically used at very low concentrations ranging from 0.005 mol % to about 0.1 mol % since they can be very effective but expensive.

In one or more embodiments, the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein may include one or more divalent cation oxides, such as alkaline earth oxides and/or ZnO. Such divalent cation oxides may be included to improve the melting behavior of the precursor glass compositions. With respect to ion exchange performance, the presence of divalent cations acts to decrease alkali mobility. When larger divalent cation oxides (such as CaO, SrO and BaO) are utilized, there may be a negative effect on ion exchange performance. Furthermore, smaller divalent cation oxides generally help develop the compressive stress in an IX glass and/or IX glass-ceramic more than the larger divalent cation oxides. Hence, divalent cation oxides such as MgO and ZnO can offer advantages with respect to improved stress relaxation, while minimizing the adverse effects on alkali diffusivity. However, when high concentrations of MgO and ZnO are utilized, there may be tendency for such divalent cation oxides to form forsterite (Mg₂SiO₄), gahnite (ZnAl₂O₄) or willemite (Zn₂SiO₄), respectively, thus causing the liquidus temperature to rise very steeply. In one or more embodiments of the glass-ceramics, glasses and/or precursor glass compositions disclosed herein may incorporate MgO and/or ZnO as the only divalent cation oxide and may, optionally, exclude other divalent cation oxides. Thus the MgO and ZnO contents of some embodiments are less than 8 mol % to maintain a reasonable liquidus temperature and in some embodiments, less than 5 mol % to enhance ion exchange performance.

In one or more embodiments, MgO may be present, in mol %, in the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein, in the range from about 0 to about 8, from about 0 to about 6, from about 0 to about 4, from about 0 to about 3.5, from about 0 to about 3, from about 0 to about 2.5, from about 0 to about 2, from about 0 to about 1.5, from about 0 to about 1, from about 0.1 to about 4, from about 0.1 to about 3.5, from about 0.1 to about 3, from about 0.1 to about 2.5, from about 0.1 to about 2, from about 0.1 to about 1.5, from about 0.1 to about 1, from about 0.5 to about 3.5, from about 1 to about 3, from 1.5 to about 2.5, from about 2 to about 6, or from about 2 to about 4, and all ranges and sub-ranges therebetween. In some embodiments, the amount of MgO may be about 2 mol % or greater, or about 2.4% or greater for the formation of armalcolite.

In one or more embodiments, ZnO may be present, in mol %, in the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein, in the range from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3.5, from about 0 to about 3, from about 0 to about 2.5, from about 0 to about 2, from about 0 to about 1.5, from about 0 to about 1, from about 0.1 to about 5, from about 0.1 to about 4, from about 0.1 to about 3.5, from about 0.1 to about 3, from about 0.1 to about 2.5, from about 0.1 to about 2, from about 0.1 to about 1.5, from about 0.1 to about 1, from about 0.5 to about 4.5, from about 1 to about 4, from 1.5 to about 3.5, or from about 2 to about 3, and all ranges and sub-ranges therebetween.

One or more embodiments of the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein may include P₂O₅. For example, P₂O₅ may be present, in mol %, in an amount in the range from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0.1 to about 10, from about 0.1 to about 9 from about 0.1 to about 8, from about 0.1 to about 7, from about 0.1 to about 6, from about 0.1 to about 5, from about 1 to about 10, from about 1 to about 9, from 1 to about 8, from about 1 to about 7, from about 1 to about 6, from about 1 to about 5, from about 1.5 to about 10, from about 2 to about 10, from about 2.5 to about 10, from about 3 to about 10, from about 3.5 to about 10, from about 4 to about 10, from about 4.5 to about 10, from about 5 to about 10, from about 5.5 to about 10, from about 6 to about 9.5, from about 6 to about 9, from about 6 to about 8.5, or from about 6 to about 8 and all ranges and sub-ranges therebetween. P₂O₅ increases the rate of ion exchange, softens the precursor glass, improves the damage resistance, and also controls the color of the resulting glass-ceramic. In some embodiments, P₂O₅ is present in an amount of less than about 12 mol % to prevent excessive softening of the precursor glass. At amounts of P₂O₅ less than about 6 mol %, the resulting glass-ceramics tend to exhibit a yellow, blue or brown color or tint depending on how much TiO₂ and P₂O₅ are present and the damage resistance decreases. In one or more embodiments, the amount of P₂O₅ is maintained in the range from about 6 mol % to about 9 mol %.

One or more embodiments of the glass-ceramic (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein may include B₂O₃. For example, B₂O₃ may be present, in mol %, in an amount of up to 1 or, alternatively, in mole in the range from about 0 to about 12, from about 0 to about 10, from about 0 to about 8, from about 0 to about 6, from about 0 to about 4, from about 0 to about 2, from about 0.1 to about 12, from about 0.1 to about 10, from about 0.1 to about 8, from about 0.1 to about 6, from about 0.1 to about 4, from about 0.1 to about 2, from about 0.01 to about 1, from about 0.1 to about 1, from about 1 to about 12, from about 2 to about 12, from about 2 to about 10, from about 2 to about 5, from about 1 to about 3, from about 2 to about 4, from about 8 to about 12, from about 8 to about 10, from about 9 to about 10, or from about 4 to about 10 and all ranges and sub-ranges therebetween.

In one or more embodiments, the amount of B₂O₃ and/or P₂O₅ may be adjusted based on the desired damage resistance of the glass and/or the glass-ceramic. Without being bound by theory, B₂O₃ and P₂O₅ can decrease the melting viscosity and effectively help to suppress zircon breakdown viscosity (i.e., the viscosity at which zircon breaks down to form ZrO₂). P₂O₅ can improve the diffusivity and decrease ion exchange times. However, in some instances, the floppy structure formed by boron and phosphorus sacrifice some compressive stress capability, and this effect can be pronounced due to the presence of P₂O₅. The inclusion of P₂O₅ yields glass-ceramics that have a white color. In some embodiments, the inclusion of specific amounts of B₂O₃ may lead to glass-ceramics having a bluish grey color.

In some embodiments, the addition of B₂O₃ into the precursor glass improves the damage resistance of the resulting glass. When boron is not charge balanced by alkali oxides or divalent cation oxides, it will be in a trigonal coordination state, which can open up the glass structure. The network around the trigonal coordinated boron is not as rigid as the network around tetrahedrally coordinated boron because the bonds in the network around trigonal coordinated boron tend to be less rigid or even floppy, and therefore the glasses can tolerate some deformation before crack formation. The amount of boron should be limited to prevent reduction in viscosity at liquidus temperature, which could preclude the use of fusion forming and other such forming methods.

The glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) according to one or more embodiments may further include a non-zero amount of SnO₂ up to about 2 mol %. For example, SnO₂ may be present in the range from about 0 to about 2, from about 0 to about 1, from about 0.01 to about 2, from about 0.01 to about 1, from about 0.1 to about 2, from about 0.1 to about 1, or from about 1 to about 2, and all ranges and sub-ranges therebetween. SnO₂ serves as a fining agent to reduce bubbles and improve glass quality, but can compete with TiO₂ solubility at high concentrations. In embodiments where SnO₂ is used as a fining agent, it may be present in the range from about 0.01 mol % to about 2 mol % or from about 0.07 mol % to about 1.2 mol % to improve quality without negatively impacting TiO₂ solubility and liquidus.

The glass-ceramics (and/or the precursor glass composition and/or glass that includes such a composition) disclosed herein may be essentially free of As₂O₃ and Sb₂O₃. As used herein, the term “essentially free of As₂O₃ and Sb₂O₃” means that the glass-ceramic article (or the glass composition) comprises less than about 0.1% by weight of either of As₂O₃ or Sb₂O₃.

In one or more embodiments, the glass-ceramic may comprise a non-zero weight percent of total crystalline phase up to about 20% by weight. In one or more embodiments, the total crystalline phase may be present, in wt. %, in the glass-ceramic in the range from about 0.1 to about 20, from about 0.1 to about 18, from about 0.1 to about 16, from about 0.1 to about 14, from about 1 to about 20, from about 2 to about 20, from about 4 to about 20, from about 6 to about 20, from about 8 to about 20, from about 10 to about 20, from about 1 to about 9, from about 2 to about 8, from about 3 to about 7, from about 4 to about 7, from about 5 to about 7, or from about 6 to about 7, and all ranges and sub-ranges therebetween. In one or more embodiments, the total crystalline phase may include about 12 wt. % or less, or about 5 wt. % or less of the glass-ceramic article. The amount of components in the precursor glass composition may be adjusted to form the desired amount of total crystalline phase. In one or more specific embodiments, the amount of TiO₂ may be adjusted to provide a desired amount of crystalline phase. Without being bound by theory, the portion of the crystalline phase disclosed herein provides a glass-ceramic that behaves like a glass. For example these low crystallinity glass-ceramics can be reformed, bent, or fused after the part has been cerammed the glass phase predominates the weight percent and thus determines most of the thermophysical properties of the glass-ceramic. In some embodiments, the crystalline phase may be considered low such that crystals may be small in size or not even present in local areas. In one or more specific embodiments, the crystals in some local areas may have one or more dimensions with a size on the nanometer scale. In the embodiments disclosed herein, the glass-ceramics may be formed using fusion forming techniques or other techniques that require the material being formed to exhibit glass-like properties or properties typically exhibited by glass materials.

In one example, the glass-like properties exhibited by the glass-ceramics disclosed herein include improved indentation crack initiation load performance. Without being bound by theory, one or more embodiments of the glass-ceramics disclosed herein exhibit glass-like properties because the indentation crack initiation load results are similar to the results obtained when glass materials are tested in the same manner. Accordingly, the glass-ceramics according to one or more embodiments exhibit a greater glass phase than other known glass-ceramics and thus can be formed using known glass forming techniques that may be otherwise unavailable if a greater crystalline phase weight percent or larger crystals were present. In known glass-ceramics having a greater amount of crystalline phase (in wt. %), the crystals present may be more numerous or may be larger in size in the precursor glass composition and, therefore, the processes available for forming the glass-ceramic may be limited due the presence of the crystals and/or crystalline phase.

In one or more embodiments, the predominant crystalline phase may include anatase, rutile, armalcolite or a combination thereof. As used herein, the phrase “predominant crystalline phase” means that such a crystalline phase constitutes the greatest percent weight of the all the crystalline phases in the glass-ceramics described herein. For example, in one or more embodiments an anatase crystalline phase may comprise the greatest percent by weight of all of the crystalline phases in the glass-ceramic. In other embodiments, a rutile crystalline phase may comprise the greatest percent by weight of all of the crystalline phases in the glass-ceramic articles. In yet other embodiments, a combination of any two or all three of an anatase crystalline phase, a rutile crystalline phase and an armalcolite crystalline phase may comprise the greatest percent by weight of all of the crystalline phases in the glass-ceramic articles.

In one or more specific embodiments, anatase, rutile and armalcolite may be present, either individually or in combination, in an amount up to 100 wt. % of the total crystalline phase of the glass-ceramics. In one or more alternative embodiments, anatase, rutile and armalcolite may be present either individually or in combination, in an amount, in wt. % of the total crystalline phase, in the range from about 0.1 to about 90, from about 1 to about 90, from about 1 to about 80, from about 1 to about 70, from about 1 to about 60, from about 10 to about 100, 20 to about 100, from about 30 to about 100, from about 40 to about 100, from about 20 to about 90, from about 30 to about 80, from about 40 to about 70, from about 50 to about 60, or from about 30 to about 40, and all ranges and sub-ranges therebetween.

The amount of anatase, rutile and/or armalcolite in the total crystalline phase may be modified by adjusting the amount of TiO₂ and/or B₂O₃ in the precursor glass composition. If the amount of TiO₂ is reduced, other crystalline phases other than rutile, anatase and/or amalcolite may form in the glass-ceramic. As otherwise described herein, other crystalline phases other than anatase and/or rutile and/or armalcolite may exhibit lower refractive index and thus provide glass-ceramics that may not exhibit the same brightness or whiteness as glass-ceramics containing anatase and/or rutile and/or armalcolite as the predominant crystalline phase(s). For example, the high refractive index of armalcolite, which is typically about 2.3, provides a white opaque color in the glass ceramics. In some instances the combined amount of any one or more of anatase, rutile and armalcolite is limited to less than about 20 wt %, less than about 15 wt %, less than about 12 wt %, less than about 10 wt % or less than about 5 wt %, but is greater than about 0.1 wt. %, of the glass-ceramic.

In some embodiments, the crystals present in the predominant crystal phase may further be characterized. The crystals may be anatase, rutile, armalcolite or a combination thereof. In some examples, at least a portion of the crystals in the predominant crystal phase have a minor dimension of about 1000 nm or less, about 500 nm or less or about 100 nm or less. In some embodiments, the minor dimension may be in the range from about 10 nm to about 1000 nm, from about 10 nm to about 500 nm, from about 10 nm to about 400 nm, from about 50 nm to about 1000 nm, from about 100 nm to about 1000 nm, form about 100 nm to about 1000 nm, form about 200 nm to about 1000 nm, from about 300 nm to about 1000 nm, from about 1 nm to about 200 nm, from about 10 nm to about 200 nm, from about 20 nm to about 200 nm, form about 30 nm to about 200 nm, from about 40 nm to about 200 nm, from about 50 nm to about 200 nm, from about 10 nm to about 100 nm, from about 50 nm to about 100 nm. The at least a portion of the crystals in the predominant phase may have an aspect ratio defined as the ratio of a major dimension of the crystal to the minor dimension of the crystal. In some instances, the aspect ratio may be about 2 or greater, or about 5 or greater.

Other crystalline phase(s) in the glass-ceramic articles may include: nepheline, β-spodumene, β-quartz, β-eucryptite, spinel, Na₂Ca₃Al₂(PO₄)₂(SiO₄)₂, Ca(PO₃)₂, Ca₂SiO₄, Ca₂₆Mg_(0.4)(PO₄)₂ and the like. In one or more embodiments, the crystalline phase(s) other than anatase, rutile and/or armalcolite may be characterized as minor. In one or more embodiments, the amount of minor crystalline phases may be minimized to provide a glass-ceramic exhibiting a bright white color. Without being bound by theory, it is believed that minor crystalline phases, such as those described herein, may introduce other colors or optical properties that are not as desirable. In one or more embodiments, the minor crystalline phases may exhibit a lower refractive index that does not provide the bright white color that maybe desired. Accordingly, in one or more embodiments, the weight percent of the minor crystalline phase(s) may be modified or even minimized to adjust the whiteness and/or brightness of the glass-ceramic. In one or more alternative embodiments, the weight percent of the minor crystalline phase(s) may be increased or decreased to adjust the mechanical properties of the glass-ceramic.

To achieve opacity, these other crystalline phases (other than rutile, anatase and/or armalcolite) may need to have a sufficient product of their size multiplied by their number density to achieve enough optical scattering for opacity. Large crystals can serve as flaws that weaken the material and reduce their usefulness. Anatase, rutile and armalcolite however, have a high refractive index, birefringence, and often grow in elongated needle like crystals which impart optical opacity at lower weight percent fraction. Since anatase, rutile and armalcolite scatter so efficiently, opaque materials can be made with small crystals so that the mechanical strength of the glass-ceramic is not degraded. Furthermore, the elongated grains of anatase, rutile and armalcolite help to toughen the glass-ceramic. For example, as shown in FIG. 1, fracture toughness increases as the amount of TiO₂ is increased.

The glass-ceramics disclosed herein may exhibit opaqueness and an average % opacity≥85% for a 0.8 mm thickness over the wavelength range from about 380 nm to about 780 nm. In one or more embodiments, the average opacity is 86% or greater, 87% or greater, 88% or greater 89% or greater, greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97% and even greater than about 98%, over the visible wavelength range of 380 nm to about 780 nm. Opacity is measured using a contrast ratio method with a spectrophotometer (for example, spectrophotometers supplied by X-rite under the model number Color i7) and different illuminants (e.g., F02, D65, A-10). The opacity of samples was measured over both a light colored backing and a dark colored backing.

The glass-ceramics described herein may be characterized by the processes by which they can be formed. Such glass-ceramics may be formed by float processes, fusion processes, slot draw process, thin rolling processes, or a combination thereof. In some embodiments, the glass-ceramic may be shaped into or have a three-dimensional shape. In one or more embodiments, the properties of the precursor glass composition and glass (e.g., viscosity) used to form the glass-ceramic may determine this processing flexibility.

In still further aspects, at least a portion of a surface of the glass-ceramics and/or precursor glasses can be strengthened, for example, by an IX process. In other words, at least a portion of the surface of the glass-ceramics and/or precursor glasses described herein are ion exchangeable or adapted to IX treatment thus yielding an IX glass-ceramic or IX glass. In one or more embodiments, the IX glass-ceramic and/or IX glass may include a CS layer extending from a surface of the glass-ceramic and/or glass to a DOL within the glass-ceramic and/or glass. In one variant, the CS layer may exhibit a compressive stress of at least about 200 MPa, at least about 250 MPa, at least about 300 MPa, at least about 350 MPa, at least about 400 MPa, at least about 450 MPa, at least about 500 MPa, at least about 550 MPa, at least about 600 MPa, at least about 650, at least about 700 MPa, and all ranges and sub-ranges therebetween. In another embodiment, the DOL may be about 15 μm or greater, about 20 μm or greater, about 25 μm or greater, about 30 μm or greater, about 35 μm or greater, about 40 μm or greater, about 45 μm or greater, about 50 μm or greater, or about 75 μm or greater. The upper limit may be up to and including about 100 μm or 150 μm and all ranges and sub-ranges therebetween.

In one or more embodiments, the glass-ceramic is IXable at a higher rate than other glass-ceramic articles made from compositions that differ from the compositions disclosed herein. As otherwise mentioned herein, in one or more embodiments, the inclusion of P₂O₅ facilitates faster ion exchange as compared to other precursor glass composition and/or glass that includes such compositions, which do not include P₂O₅.

It is noted that in addition to single step IX processes, multiple IX procedures might be utilized to create a designed IX profile for enhanced performance. That is, a stress profile created to a selected DOL by using IX baths formulated with differing concentration of ions or by using multiple IX baths formulated using different ion species having different ionic radii.

The glass-ceramics according to one or more embodiments may exhibit superior mechanical properties. For example, the glass-ceramic article may exhibit a high crack initiation threshold, as measured using a Vickers indenter (“Vickers indentation crack initiation threshold”). Such glass-ceramics may be IX glass-ceramic articles. In one or more embodiments, the glass-ceramics may exhibit a Vickers indentation crack initiation load of at least about 10 kgf In one or more specific embodiments, the glass-ceramics may exhibit a Vickers indentation crack initiation load of at least about 15 kgf or even at least about 20 kgf. Such glass-ceramics may be IX glass-ceramics that are ion exchanged, as described herein, for 1 hour, 2 hours or 4 hours, in a bath having a temperature of about 410° C.

In one or more embodiments, the glass-ceramic may exhibit a white color or may be characterized as essentially white. As used herein, the term “essentially white” means that the glass-ceramic has a color presented in CIELAB color space coordinates determined from specular reflectance measurements using a spectrophotometer and different illuminants. For example, as measured using illuminant D65, the glass-ceramic may exhibit CIELAB color coordinates of CIE a* in the range from about −2 to about 8; CIE b* in the range from about −7 to about 30; and CIE L* in the range from about 85 to about 100. In some embodiments, the glass-ceramic may exhibit CIELAB color coordinates of CIE a* in the range from about −1 to about 0, CIE b* in the range from about −8 to about −3, and CIE L* in the range from about 80 to about 100, as measured using a spectrophotometer with illuminant F02 or D65. These values may be obtained when specular reflectance is included or excluded during measurement. Moreover, the glass-ceramics exhibit an essentially white color even when processing conditions utilized to form the glass-ceramics vary. For example, the glass-ceramics exhibit an essentially white color even when heat treatment temperature(s) vary by as much as 100° C. In one variant, the essentially white color is exhibited by the glass-ceramics when heat treatment temperatures vary by more than 5° C., 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C. and 95° C.

In one or more embodiments, the glass-ceramic may exhibit a color or tint, other than white. In such embodiments, colorants in the form of metallic ions may be present in the precursor glass such as transition metal ions and oxides of Co, Cr, Cu, Sn, Mn, Sb, Fe, Bi, Ni, V, Se and others known in the art.

Precursors Glass Compositions and Glasses

A second aspect of this disclosure pertains to the precursor glass compositions and glasses including the same utilized to form the glass-ceramics described herein. The glass-ceramics according to one or more embodiments may be formed from a glass, such as an aluminosilicate glass, having a precursor glass composition as otherwise described herein with respect to the glass-ceramics.

In one or more embodiments, the glass composition exhibits a liquidus viscosity of about 20 kP or greater and a liquidus temperature of less than about 1400° C. when formed into a glass article via, for example, down drawing. The precursor glass compositions may be formed into a glass article that also exhibits a liquidus viscosity of at least about 20 kilopoise (kP) and a liquidus temperature of less than about 1400° C. In one variant, the glass composition and/or glass including such composition may exhibit a liquidus viscosity of at least about 20 kP or greater, 22 kP or greater, 24 kP or greater, 26 kP or greater, 28 kP or greater, 30 kP or greater, or about 50 kP or greater, including all ranges and sub-ranges therebetween. In another variant, the glass composition and/or glass including such composition may exhibit a liquidus temperature of about 1350° C. or less, 1300° C. or less, 1250° C. or less, 1200° C. or less, 1150° C. or less, 1100° C. or less, 1050° C. or less, 1000° C. or less, 950° C. or less, 900° C. or less, and all ranges and sub-ranges therebetween. The precursor glass compositions and glass that includes such compositions may be described as crystallizable. In some embodiments, the glass composition may be characterized as formable by a fusion draw process, formable by a slot draw process, formable by a float process, formable by a thin rolling process, or a combination thereof. In some embodiments, the glass may be shaped into or have a three-dimensional shape.

A third aspect of the present disclosure pertains to a method for forming precursor glasses formulated to be crystallizable to glass-ceramics and methods for forming glass-ceramics having a anatase, rutile, armalcolite or a combination thereof as the predominant crystalline phase. In one or more embodiments, the methods included melting a batch for, and forming, a glass having a composition as otherwise described herein. For example, the composition may include in mol %: SiO₂ in the range from about 45 to about 75; Al₂O₃ in the range from about 4 to about 25; P₂O₅ in the range from about 0.1 to about 10; MgO in the range from about 0.01 to about 8; R₂O in the range from about 0 to about 33; ZnO in the range from about 0 to about 8; ZrO₂ in the range from about 0 to about 4, B₂O₃ in the range from about 0 to about 12, and one or more nucleating agents in the range from about 0.5 to about 12. In one or more embodiments, the composition may include one or more colorants in the form of metallic ions, such as transition metal ions and oxides of Co, Cr, Cu, Sn, Mn, Sb, Fe, Bi, Ni, V, Se and others known in the art.

In addition, the batch is formulated to produce the precursor glass articles and compositions described herein, which, upon fining and homogenization, form molten glass compositions at a temperature below about 1600° C. Still yet other aspects of the method include forming molten precursor glasses into the glass article described herein. The method may further include ceramming the glass for a period of time to cause the generation of a glass-ceramic which includes a predominant crystalline phase comprising anatase, rutile, armalcolite or a combination thereof; and cooling the glass-ceramic to room temperature. Forming the glass may include down drawing (by either a slot draw or fusion draw process), float processing, or thin rolling the glass. In some embodiments, the method may include shaping the glass or glass-ceramic to a three-dimensional shape.

In one or more embodiments, the precursor glass composition exhibits a liquidus viscosity of about 10 kilopoise (kP) or greater (e.g., 20 kP or greater, 50 kP or greater or 100 kP or greater) and a liquidus temperature of less than about 1400° C. during forming (e.g., down drawn).

Regarding raw material selection it is recommended that low iron content sand is used as the SiO₂ source. Prior acid treatment may be necessary to reduce the iron level of the sand and other batch materials. It is important to make sure that the treatment of the batch materials per se does not introduce more than 500 ppm iron oxides. In some embodiments, raw materials that contribute less than 200 ppm total Fe₂O₃ to the glass and glass-ceramic may be utilized, if a bright white glass-ceramic is desired. Anhydrous boric acid may be used as the source of B₂O₃. One skilled in the art can calculate the amount of batch materials used according to the projected final composition of the glass-ceramic. As mentioned above, a fining agent that has been found to be beneficial is SnO₂ in a non-zero amount up to 2 mole %.

The mixed batch materials are then charged into a glass tank and melted according to conventional glass melting process. One skilled in the glass melting art can adjust the composition of the batch within the above described compositional range to fine tune the melting ease of the glass in order to accommodate the operating capacity and temperature of the glass melting tank. The molten glass can be homogenized and fined using conventional methods.

The homogenized, fined and thermally uniform molten glass is then formed into desired shapes. Various shaping may be used, such as casting, molding, pressing, rolling, floating, and the like. Generally, the glass should be formed at a viscosity lower than the liquidus viscosity (hence a temperature higher than the liquidus temperature). When pressing is utilized, the glass is first delivered to high temperature molds and formed into glass articles with desired shape, surface texture and surface roughness by using a plunger. To obtain low surface roughness and a precise surface contour, precision plungers are required to press the glass gobs filled in the molds. It is also required that the plungers will not introduce IR absorbing oxides or other defects onto the surface of the glass article should high IR transmission is required. The moldings are then removed from the molds and transferred to a glass annealer to remove enough stress in the moldings for further processing where necessary and desirable. Thereafter, the cooled glass moldings are inspected, analyzed of chemical and physical properties for quality control purpose. Surface roughness and contour may be tested for compliance with product specification.

To produce the glass-ceramic article of the present disclosure, the thus prepared glass articles are placed into a crystallization kiln to undergo the ceramming process. The temperature-temporal profile of the kiln is desirably program-controlled and optimized to ensure that the glass moldings and other glass articles, such as glass plates and the like, are formed into glass-ceramic articles described herein. As described above, the glass composition and the thermal history during the ceramming process determine the final crystalline phases, their assemblage and crystallite sizes in the final product. In one or more embodiments, the glass articles are heat treated to a temperature in the range from about 700° C. to about 1000° C. for a period of time sufficient to cause the generation of crystals and thus, a glass-ceramic. Generally, the glass articles are first heated to a nucleation temperature (Tn) range where crystal nuclei start to form. Subsequently, they are heated to an even higher maximum crystallization temperature Tc to obtain the desired crystalline phase(s). It is often desired to keep the articles at Tc for a period of time so that crystallization reaches a desired extent. In order to obtain the glass-ceramic articles of the present disclosure, the nucleation temperature Tn is in the range from about 700° C. to about 800° C., and the crystallization temperature Tc is in the range from about 800° C. to about 1000° C. After crystallization, the articles are allowed to exit the crystallization kiln and are cooled to room temperature. One skilled in the art can adjust Tn, Tc and the temperature-temporal profile of the crystallization cycle to accommodate the different glass compositions within the above-described range. The glass-ceramic article of the present disclosure can advantageously exhibit an opaque white coloring.

In one or more embodiments, the method includes (i) heating the glass at a rate of about 5° C./min to a nucleation temperature (Tn) ranging between 700° C. and 800° C. or until the glass exhibits a viscosity from about 10⁹ to about 10¹³ poise (e.g., from about 10¹⁰ to about 10¹² poise); (ii) maintaining the glass at the nucleation temperature for a time ranging between 1 h to 8 h (or specifically from about 1 h to about 4 h) to produce a nucleated glass; (iii) heating the nucleated glass at a rate of about 5° C./min to a crystallization temperature (Tc) ranging between about 50° C. greater than an annealing temperature of the glass (e.g., 800° C.) and about 1100° C. or until the nucleated glass exhibits a viscosity from about 10⁷ to about 10¹² poise (e.g., from about 10⁸ poise to about 10¹¹ poise); (iv) maintaining the nucleated glass at the crystallization temperature for a time ranging between about 2 h to about 8 h (or more specifically from about 2 h to about 4 h) to produce an article comprising and/or a glass-ceramic as described herein; and (v) cooling the article comprising and/or glass-ceramic to room temperature. The viscosity and/or temperatures to which the glass or nucleated glass is heated may be adjusted to maintain the desired shape of the glass or glass-ceramic. The opacity of the resulting glass-ceramic may be modified by modifying the ceramming temperatures and/or times. For example, lighter opals (or less opaque glass-ceramics) may be formed using lower nucleation and/or crystallization temperatures and shorter nucleation and/or crystallization times, and more opaque glass-ceramics can be formed using higher nucleation and/or crystallization temperatures and longer nucleation and/or crystallization times. As otherwise described herein, the amount of nucleating agent may also be adjusted to modify the opacity.

Temperature-temporal profile of steps (iii) and (iv), in addition to the composition of the precursor glass are judiciously prescribed so as to produce the desired crystalline phase(s); desired total weight of crystalline phase; desired proportions of the predominate crystalline phase and/or minor crystalline phase(s) and residual glass; desired crystal phase assemblages of the predominate crystalline phase and/or minor crystalline phase(s) and residual glass; desired grain sizes or grain size distributions among the predominate crystalline phase and/or minor crystalline phase(s); and, hence the final integrity, quality, color, and/or opacity, of resultant glass-ceramics and/or glass-ceramic articles according to aspects and/or embodiments of this disclosure.

The method may include subjecting the glass-ceramic to ion exchange treatment to provide an IX glass-ceramic. In one or more alternative embodiments, the method includes subjecting the glass article to ion exchange treatment to provide an IX glass article, prior to ceramming the glass article or even without ceramming the glass article. In one or more embodiments, the precursor glass may also be subjected to ion exchange treatment to provide an IX glass. In one or more embodiments, potassium (K) ions, for example, could either replace, or be replaced by, sodium (Na) ions in the glass-ceramic (and/or glass article), again depending upon the IX temperature conditions. Alternatively, other alkali metal ions having larger atomic radii, such as (Rb) rubidium or cesium (Cs) could replace smaller alkali metal ions in the glass-ceramic (and/or glass article). Similarly, other alkali metal salts such as, but not limited to, sulfates, halides, and the like may be used in the ion exchange process.

It is contemplated that both types of ion exchange can take place; i.e., larger for smaller ions are replaced and/or smaller for larger ions are replaced. In one or more embodiments, the method involves ion exchanging (particularly sodium-for-potassium ion exchange) the glass-ceramic article (and/or glass article) in a KNO₃ bath at temperatures from about 300° C. to about 500° C. (e.g., from about 360 to about 450° C.) for up to 10 h. In one some aspects and/or embodiments, the method involves ion exchanging (particularly lithium-for-sodium ion exchange) the glass-ceramic article (and/or glass article) by placing it in a NaNO₃ bath at temperatures between 330-450° C. for times up to 10 h. In other aspects and/or embodiments, the ion exchange process can be accomplished utilizing mixed potassium/sodium baths at similar temperatures and times; e.g., an 80/20 KNO₃/NaNO₃ bath or alternatively a 60/40 KNO₃/NaNO₃ at comparable temperatures. In still other aspects and/or embodiments, a two-step ion exchange process is contemplated wherein the first step is accomplished in a Li-containing salt bath; e.g. the molten salt bath can be a high temperature sulfate salt bath composed of Li₂SO₄ as a major ingredient, but diluted with Na₂SO₄, K₂SO₄ or Cs₂SO₄ in sufficient concentration to create a molten bath. This ion exchange step functions to replace the larger sodium ions in the glass-ceramic article with the smaller lithium ions which are found in the Li-containing salt bath. The second ion exchange step functions to exchange Na into the glass-ceramic article (and/or glass article) and can be accomplished as above by a NaNO₃ bath at temperatures between 320° C. and 430° C. The glass-ceramic can also be ion exchanged in a bath containing Ag or Cu ions to impart antimicrobial or antiviral properties to the material.

In one or more embodiments, the glass-ceramic (and/or glass article) is subjected to IX treatment to form an IX glass-ceramic article (and/or glass article) having at least a portion of at least one surface subjected to an IX process, such that the IX portion of the least one surface exhibits a CS layer having a DOL greater than or equal to 2% of the overall article thickness while exhibiting a compressive stress (σ_(s)) in the surface of at least 300 MPa. Any IX process known to those in the art might be suitable as long as the above DOL and compressive stress (σ_(s)) are achievable.

In a more particular embodiment, the glass-ceramics described herein may be incorporated into a housing or enclosure of a device and may exhibit an overall thickness of 2 mm and a CS layer with a DOL of about 40 μm or greater and a compressive stress (σ_(s)) of about 500 MPa or greater. Again any IX process which achieves these features is suitable.

It is noted that in addition to single step IX processes, multiple IX procedures might be utilized to create a designed IX profile for enhanced performance. That is, a stress profile created to a selected DOL by using IX baths formulated with differing concentration of ions or by using multiple IX baths formulated using different ion species having different ionic radii.

The resulting glass-ceramic, made according to one or more embodiments of the method, may exhibit a color presented in CIELAB color space coordinates determined from specular reflectance measurements using a spectrophotometer with various illuminants (e.g, with illuminant D65 or F02). Specular reflectance may be included or excluded in the measurements, as otherwise described herein. In one or more embodiments, the ion exchange treatment is more effective due to the low amount of total crystalline phase in the glass-ceramics disclosed herein. It is believed that the low amount of total crystalline phase leaves a greater portion of glass in the glass-ceramic, which can undergo strengthening via ion exchange. Without being bound by theory, in one or more embodiments, subjecting the glasses or glass-ceramics disclosed herein to an ion exchange process in a molten salt bath of KNO₃ and temperature of about 430° C. for up to 16 hours resulted in glass-ceramics exhibiting high indentation crack initiation load values (e.g., from about 10 kgf to about 15 kgf). Without being bound by theory, it is believed that a fast cooling process (during the ceramming process) leads to a higher fictive temperature in the precursor glass, which is believed to result in improved crack resistance (in the form of improved indentation crack initiation load) in substrates that are ion exchanged. Accordingly, subjecting the precursor glasses to a fictivation process or by forming using a fusion process (which has a fast cooling rate), may also result in glass-ceramics exhibiting improved indentation crack initiation load.

In the following examples, various characterizations of the precursor glass composition, precursor glasses and glass-ceramics will be described. The characterizations may include CIELAB color space coordinates, translucency, opacity, viscosity, annealing point, strain point, dielectric parameters, identity of the crystalline phases and/or crystal sizes, elemental profiles, compressive stress profiles, Vickers hardness, CTE, fracture toughness (K_(1C)).

CIELAB color space coordinates (e.g., CIE L*; CIE a*; and CIE b*; or CIE L*, a*, and b*; or L*, a*, and b*) for describing the color of the glass-ceramics; described herein were determined by methods known to those in the art from total reflectance—specular included—measurements or reflectance with specular reflectance excluded.

Viscosity of precursor glasses according to aspects and/or embodiments of this disclosure can be by methods known to those in the art, such as, those described in ASTM C965-96 and ASTM C1350M-96.

Annealing point and strain point of precursor glasses described herein can be measured by methods known to those in the art, such as, those described in ASTM C598 (and its progeny, all herein incorporated by reference) “Standard Test Method for Annealing Point and Strain Point of Glass by Beam Bending,” ASTM International, Conshohocken, Pa., US.

Identity of the crystalline phases of crystal phase assemblages and/or crystal sizes of a crystalline phase were determined by X-ray diffraction (XRD) analysis techniques known to those in the art, using such commercially available equipment as the model as a PW1830 (Cu Kα radiation) diffractometer manufactured by Philips, Netherlands. Spectra were typically acquired for 2θ from 5 to 80 degrees.

Elemental profiles measured for characterizing surfaces of precursor glasses, and glass-ceramics were determined by analytical techniques know to those in the art, such as, electron microprobe (EMP); x-ray photoluminescence spectroscopy (XPS); secondary ion mass spectroscopy (SIMS) . . . etc.

The compressive stress (σ_(s)) of the surface CS layer, average surface compression, and DOL of the glass-ceramics and precursor glasses described herein can be conveniently measured using conventional optical techniques and instrumentation such as commercially available surface stress meter models FSM-30, FSM-60, FSM-6000LE, FSM-7000H . . . etc. available from Luceo Co., Ltd. and/or Orihara Industrial Co., Ltd., both in Tokyo, Japan. In some instances, additional analysis may be required to determine an accurate stress profile.

Vickers hardness of precursor glasses and/or glass-ceramics can be characterized by methods known to those in the art, such as, those described in ASTM C1327 (and its progeny, all herein incorporated by reference) Standard Test Methods for Vickers Indentation Hardness of Advanced Ceramics,” ASTM International, Conshohocken, Pa., US.

Coefficient of thermal expansion (CTE) of precursor glasses and/or glass-ceramics can be characterized by methods known to those in the art, such as, those described in ASTM E228 (and its progeny, all herein incorporated by reference) Standard Test Method for Linear Thermal Expansion of Solid Materials with a Push-Rod Dilatometer,” ASTM International, Conshohocken, Pa., US.

Fracture toughness (K_(1C)) of precursor glasses and/or glass-ceramics can be characterized by methods known to those in the art, such as, those described in ASTM C1421 (and its progeny, all herein incorporated by reference) Standard Test Methods for Determination of Fracture Toughness of Advanced Ceramics at Ambient Temperature,” ASTM International, Conshohocken, Pa., US and/or using chevron notched short bar (CNSB) specimens and/or methods substantially according to ASTM E1304 C1421 (and its progeny, all herein incorporated by reference) “Standard Test Method for Plane-Strain (Chevron-Notch) Fracture Toughness of Metallic Materials,” ASTM International, Conshohocken, Pa., US.

EXAMPLES

Various embodiments will be further clarified by the following examples, which are in no way intended to limit this disclosure thereto.

Inasmuch as the sum of the individual constituents totals or very closely approximates 100, for all practical purposes the reported values may be deemed to represent mole %. The actual precursor glass batch ingredients may comprise any materials, either oxides, or other compounds, which, when melted together with the other batch components, will be converted into the desired oxide in the proper proportions.

Examples 1-116: The exemplary precursor glass precursors listed in Table I were made in a platinum crucible using a batch of raw materials formulated to yield 1000 g of precursor glass upon melting and refining. Each crucible containing a formulated raw materials batch was placed in a furnace preheated to from 1575° C.-1650° C., the formulated raw materials batch melted and refined to produce molten precursor glass that was then cast as patties of precursor glass that were annealed for 1 hour at or around the annealing point of the glass composition. In this way individual patties of an exemplary precursor glass could then be cut into multiple pieces and the one or more of the pieces were subjected to a number of different and/or similar thermal treatments (nucleated and crystallized) by placing in a static furnace programmed with such different or similar temperature-temporal cycle. Examples of some of the temperature-temporal cycles to which a number of the patties of the exemplary precursor glasses listed in Table I were subjected included:

i) introduction of the patties into a furnace set at between room temperature and 500° C.;

ii) heat treatment at 5° C./minute (min) to the nucleation temperature (Tn), as shown in Table III (e.g., 750° C.);

iii) hold at Tn for 2 h;

iv) heat at 5° C./min from Tn to the crystallization temperature (Tc), as shown in Table III (e.g., 850° C.-1050° C.); and

v) hold for 4 h the crystallization temperature (Tc); and

vi) cool to room temperature.

Thermally treated patties of precursor glasses listed in Table I, following thermal treatment as described above to glass-ceramics, were also analyzed for the properties listed in Table I. The precursor glasses listed in Table I were analyzed by X-ray Fluorescence (XRF) and/or by ICP or as batched to determine the components of the precursor glasses. Anneal, strain and softening points were determined by fiber elongation. Density was determined by Buoyancy Method. Each coefficient of thermal expansion (CTE) value is the average value between room temperature and 300° C. Elastic modulus for each precursor glass was determined by resonant ultrasound spectroscopy. Refractive index for each precursor glass is stated for a wavelength of 589.3 nm. Stress optic coefficient (SOC″) values were determined by the diametral compression method. Liquidus temperature measurements were reported based on 24 hour and 72 hour gradient boat testing.

TABLE I Table I: Precursor glass compositions. Example = 

Oxide [mole %] 1 2 3 4 5 SiO₂ 60.42 59.42 58.36 58.36 58.34 Al₂O₃ 14.98 14.98 15.46 15.46 14.96 P₂O₅ 4.99 4.99 4.99 4.99 4.98 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 2 0.00 Na₂O 14.98 14.98 16.05 14.06 15.56 K₂O 0.00 0.00 0.00 0.00 0.00 MgO 2.49 2.5 2.99 2.99 4.00 CaO 0.06 0.06 0.06 0.05 0.06 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 2.00 3.00 1.99 1.99 2.00 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.08 0.08 0.10 0.10 0.10 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 0.00 0.00 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] 0.00 0.00 0.59 0.60 0.60 Strain Pt (C.): 612 587 619 Anneal Pt (C.): 659 632 664 Softening Pt (C.): 918 887 930 CTE (×10{circumflex over ( )}−7/C.): 83 81.6 81.8 Density (g/cm{circumflex over ( )}3): 2.441 2.439 2.444 Poisson's Ratio: 0.218 0.169 0.202 Shear Modulus (Mpsi): 4.039 4.248 4.042 Young's Modulus (Mpsi): 9.836 9.929 9.715 Refractive Index: 1.5047 1.4965 1.4944 Stress optic coefficient Fracture toughness (MPa/m1/2) 0.684 0.709 0.638 Hardness (MPa) 536 552 536 Liquidus temperature 1105 1110 1130 1130 1120 Fulcher_A −3.779 Fulcher_B 9595 Fulcher_T0 83.8 Example = 

Oxide [mole %] 6 7 8 9 10 SiO₂ 59.48 56.02 55.02 56.02 55.02 Al₂O₃ 14.38 15.28 15.00 15.27 15.00 P₂O₅ 5.67 7.41 7.28 5.56 7.28 B₂O₃ 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 Na₂O 15.48 14.83 14.54 14.83 14.54 K₂O 0.00 0.47 0.45 0.47 0.45 MgO 2.89 0.36 0.36 0.38 0.36 CaO 0.00 3.71 3.63 3.70 3.63 ZnO 0.00 0.00 0.00 BaO 0.00 0.00 0.00 TiO₂ 2.00 1.85 3.63 3.71 3.63 TeO₂ 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 SnO₂ 0.10 0.07 0.07 0.08 0.07 ZrO₂ 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 F— 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 [R₂O—Al₂O₃] 1.10 0.02 −0.01 0.03 −0.01 Strain Pt (C.): 611 610 604 Anneal Pt (C.): 655 665 656 Softening Pt (C.): 921 930 917 CTE (×10{circumflex over ( )}−7/C.): 79.8 85.8 86 Density (g/cm{circumflex over ( )}3): 2.43 2.447 2.463 Poisson's Ratio: 0.209 0.233 0.278 Shear Modulus (Mpsi): 4.261 4.228 4.036 Young's Modulus (Mpsi): 10.301 10.423 10.313 Refractive Index: 1.4971 1.5077 1.5057 Stress optic coefficient Fracture toughness (MPa/m1/2) 0.75 0.742 0.737 Hardness (MPa) 564 557 537 Liquidus temperature 1090 1170 1140 1155 1130 Fulcher_A −2.992 −1.968 −2.401 −2.985 Fulcher_B 7985.9 5460.4 6257.2 7468.4 Fulcher_T0 155.5 341 248.1 170 Example = 

Oxide [mole %] 11 12 13 14 15 SiO₂ 54.03 56.04 55.00 55.01 57.56 Al₂O₃ 14.74 15.28 14.55 15.46 15.70 P₂O₅ 8.93 7.41 7.27 7.27 7.62 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 14.29 14.81 15.00 14.09 15.23 K₂O 0.44 0.46 0.46 0.45 0.48 MgO 0.35 0.37 0.36 0.36 0.38 CaO 3.57 1.85 3.64 3.64 1.91 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 3.57 3.70 3.63 3.63 0.95 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.07 0.07 0.07 0.07 0.08 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 0.00 0.09 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] −0.01 −0.01 0.91 −0.92 0.01 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1060 1110 1130 1110 Hardness (MPa) −2.835 Liquidus temperature 7459.3 Fulcher_A 166.7 Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 16 17 18 19 20 SiO₂ 57.36 57.08 57.07 56.55 56.04 Al₂O₃ 15.64 15.57 15.57 15.43 15.28 P₂O₅ 7.59 7.55 7.55 7.48 7.41 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 15.17 15.09 15.10 14.96 14.81 K₂O 0.48 0.47 0.47 0.47 0.46 MgO 0.37 0.38 0.39 0.37 0.37 CaO 1.89 1.89 0.00 0.93 1.85 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 0.94 0.94 3.78 3.74 3.70 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.07 0.08 0.07 0.07 0.07 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.47 0.94 0.00 0.00 0.00 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] 0.01 −0.01 0.00 0.00 −0.01 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 21 22 23 24 25 SiO₂ 57.59 57.05 56.53 57.06 56.78 Al₂O₃ 15.71 15.56 15.42 15.56 15.49 P₂O₅ 7.62 7.54 7.47 7.54 7.51 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 15.23 15.09 14.94 13.68 15.01 K₂O 0.48 0.47 0.46 1.89 0.47 MgO 0.38 0.39 0.37 0.37 0.37 CaO 0.05 0.05 0.05 0.05 0.05 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 2.86 3.78 4.68 3.77 3.76 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.08 0.07 0.07 0.07 0.07 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 0.00 0.47 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] 0.00 0.00 −0.02 0.01 −0.01 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 26 27 28 29 30 SiO₂ 56.51 56.03 56.03 56.02 57.08 Al₂O₃ 15.42 15.19 15.28 15.37 15.48 P₂O₅ 7.47 7.41 7.41 7.41 7.55 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 14.94 14.91 14.82 14.73 15.19 K₂O 0.47 0.46 0.46 0.46 0.47 MgO 0.38 0.37 0.37 0.37 0.39 CaO 0.05 1.85 1.85 1.85 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 3.74 3.70 3.70 3.71 3.77 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.08 0.07 0.07 0.07 0.07 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.93 0.00 0.00 0.00 0.00 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] −0.01 0.18 0.00 −0.18 0.18 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 31 32 33 34 35 SiO₂ 57.07 57.07 57.05 57.06 57.05 Al₂O₃ 15.57 15.67 15.18 15.28 15.37 P₂O₅ 7.55 7.55 7.54 7.54 7.55 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 15.10 15.00 15.46 15.36 15.28 K₂O 0.47 0.47 0.47 0.47 0.47 MgO 0.39 0.39 0.38 0.38 0.38 CaO 0.00 0.00 0.05 0.05 0.05 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 3.78 3.78 3.78 3.77 3.77 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.07 0.07 0.07 0.07 0.07 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 0.00 0.00 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] 0.00 −0.20 0.75 0.55 0.38 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): 2.432 2.427 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1110 1125 1130 Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 36 37 38 39 40 SiO₂ 58.17 57.05 55.99 60.77 59.27 Al₂O₃ 15.76 15.47 15.18 15.94 15.94 P₂O₅ 5.76 7.54 9.26 4.98 6.48 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 15.47 15.18 14.90 16.23 16.24 K₂O 0.48 0.47 0.46 0.00 0.00 MgO 0.38 0.39 0.37 0.02 0.02 CaO 0.05 0.05 0.05 0.06 0.05 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 3.84 3.77 3.71 2.00 1.99 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.08 0.07 0.07 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 0.00 0.00 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] 0.19 0.18 0.18 0.29 0.30 Strain Pt (C.): 624 604 Anneal Pt (C.): 683 661 Softening Pt (C.): 963 946 CTE (×10{circumflex over ( )}−7/C.): 82.9 82.1 Density (g/cm{circumflex over ( )}3): 2.436 2.428 2.422 2.417 2.413 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1150 1140 1130 Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 41 42 43 44 45 SiO₂ 58.28 57.49 59.48 61.46 54.50 Al₂O₃ 15.94 15.86 14.88 13.88 18.16 P₂O₅ 6.47 6.45 6.44 6.44 7.27 B₂O₃ 0.00 0.00 0.00 0.00 0.00 Li₂O 0.00 0.00 0.00 0.00 0.00 Na₂O 16.24 16.16 15.16 14.17 18.17 K₂O 0.00 0.00 0.00 0.00 0.00 MgO 0.02 0.02 0.02 0.02 0.02 CaO 0.05 0.05 0.05 0.05 0.07 ZnO 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 2.99 3.97 3.96 3.97 1.81 TeO₂ 0.00 0.00 0.00 0.00 0.00 Nb₂O₅ 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.00 0.00 La₂O₃ 0.00 0.00 0.00 0.00 0.00 F— 0.00 0.00 0.00 0.00 0.00 CeO₂ 0.00 0.00 0.00 0.00 0.00 [R₂O—Al₂O₃] 0.30 0.30 0.28 0.29 0.01 Strain Pt (C.): 599 594 592 592 598 Anneal Pt (C.): 652 644 643 643 654 Softening Pt (C.): 924 905 911 917 927 CTE (×10{circumflex over ( )}−7/C.): 81.8 81.8 78.6 74.4 88 Density (g/cm{circumflex over ( )}3): 2.422 2.433 2.423 2.413 2.427 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1150 Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 46 47 48 49 50 SiO₂ 54.50 53.53 53.54 52.59 52.59 Al₂O₃ 18.17 17.84 17.85 17.52 17.53 P₂O₅ 7.27 7.13 7.13 7.01 7.01 B₂O₃ Li₂O Na₂O 13.62 17.84 13.38 17.53 13.15 K₂O 4.55 0.00 4.46 0.00 4.38 MgO 0.02 0.02 0.02 0.02 0.02 CaO 0.05 0.07 0.05 0.05 0.05 ZnO BaO TiO₂ 1.82 3.57 3.57 5.26 5.26 TeO₂ Nb₂O₅ SnO₂ ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.00 0.00 −0.01 0.01 0.00 Strain Pt (C.): 591 593 584 Anneal Pt (C.): 647 643 635 Softening Pt (C.): 935 898 906 CTE (×10{circumflex over ( )}−7/C.): 94.8 86.8 93.5 Density (g/cm{circumflex over ( )}3): 2.428 2.442 2.441 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 51 52 53 54 55 SiO₂ 57.05 57.05 57.05 58.93 60.83 Al₂O₃ 14.62 14.85 15.09 14.15 13.21 P₂O₅ 7.54 7.55 7.54 7.54 7.54 B₂O₃ Li₂O Na₂O 16.03 15.79 15.56 14.61 13.67 K₂O 0.47 0.47 0.47 0.47 0.47 MgO 0.38 0.38 0.38 0.38 0.38 CaO 0.05 0.05 0.05 0.05 0.05 ZnO BaO TiO₂ 3.77 3.77 3.78 3.77 3.77 TeO₂ Nb₂O₅ SnO₂ 0.07 0.07 0.07 0.08 0.08 ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 1.88 1.41 0.94 0.93 0.93 Strain Pt (C.): 569 572 572 575 576 Anneal Pt (C.): 616 619 620 624 625 Softening Pt (C.): 861 863 871 881 879 CTE (×10{circumflex over ( )}−7/C.): 85.6 84.4 82.7 79.9 76.3 Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1095 1120 1120 1115 1130 Hardness (MPa) −4.898 Liquidus temperature 13266 Fulcher_A −187.7 Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 56 57 58 59 60 SiO₂ 62.72 58.14 57.59 57.31 57.19 Al₂O₃ 12.26 15.38 15.23 15.16 15.12 P₂O₅ 7.54 7.69 7.62 7.58 7.56 B₂O₃ Li₂O Na₂O 12.72 15.86 15.71 15.63 15.61 K₂O 0.47 0.48 0.48 0.48 0.47 MgO 0.38 0.38 0.38 0.38 0.38 CaO 0.05 0.05 0.05 0.05 0.05 ZnO BaO TiO₂ 3.78 1.93 2.86 3.32 3.54 TeO₂ Nb₂O₅ SnO₂ 0.08 0.08 0.08 0.08 0.07 ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.93 0.96 0.96 0.95 0.96 Strain Pt (C.): 585 Anneal Pt (C.): 638 Softening Pt (C.): 889 CTE (×10{circumflex over ( )}−7/C.): 72 Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1140 980 1090 1110 Hardness (MPa) −3.265 −3.697 −4.622 Liquidus temperature 9524 9888 12340.5 Fulcher_A 27.3 30.5 −134.4 Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 61 62 63 64 65 SiO₂ 57.54 56.46 61.48 59.99 58.85 Al₂O₃ 15.22 14.94 13.88 14.51 15.19 P₂O₅ 7.61 7.46 6.45 6.77 6.65 B₂O₃ Li₂O Na₂O 15.69 15.39 14.19 13.85 13.57 K₂O 0.48 0.47 0.00 0.00 0.00 MgO 0.00 1.87 0.00 0.97 1.91 CaO 0.05 0.07 0.03 0.03 0.03 ZnO 0.00 0.00 0.00 BaO TiO₂ 3.33 3.27 3.97 3.88 3.80 TeO₂ Nb₂O₅ SnO₂ 0.08 0.07 ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.95 0.92 0.31 −0.66 −1.62 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: 1.5 1.5 1.5 1.5 Stress optic coefficient 33.57 33.43 33.46 Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 66 67 68 69 70 SiO₂ 58.86 58.87 60.01 56.36 57.19 Al₂O₃ 15.18 15.19 14.52 15.51 15.22 P₂O₅ 6.65 6.65 6.78 7.71 7.56 B₂O₃ Li₂O Na₂O 13.58 13.58 13.84 15.80 15.50 K₂O 0.00 0.00 0.00 0.48 0.47 MgO 0.96 0.00 0.00 0.39 0.38 CaO 0.03 0.01 0.01 0.06 0.06 ZnO 0.95 1.90 0.97 BaO TiO₂ 3.79 3.80 3.87 3.61 3.54 TeO₂ Nb₂O₅ SnO₂ 0.08 0.08 ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] −1.60 −1.61 −0.68 0.77 0.75 Strain Pt (C.): 571 572 576 Anneal Pt (C.): 618 621 623 Softening Pt (C.): 866 864 876 CTE (×10{circumflex over ( )}−7/C.): 82.3 82.9 81.1 Density (g/cm{circumflex over ( )}3): 2.433 2.43 2.428 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: 1.5 1.5 Stress optic coefficient 34.28 34.1 Fracture toughness (MPa/m1/2) 1130 1130 1120 Hardness (MPa) −3.015 −3.079 −3.095 Liquidus temperature 8087.3 8366.6 8407.1 Fulcher_A 120.9 95.8 101.8 Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 71 72 73 74 75 SiO₂ 57.59 57.98 57.19 57.19 57.19 Al₂O₃ 15.08 14.94 15.22 15.22 15.22 P₂O₅ 7.49 7.42 7.56 7.56 7.56 B₂O₃ Li₂O Na₂O 15.36 15.21 15.97 14.08 15.50 K₂O 0.47 0.46 0.00 1.89 0.47 MgO 0.37 0.37 0.38 0.38 0.38 CaO 0.06 0.06 0.06 0.05 0.06 ZnO BaO TiO₂ 3.51 3.48 3.54 3.54 3.07 TeO₂ Nb₂O₅ SnO₂ 0.07 0.07 0.08 0.08 0.08 ZrO₂ 0.47 MnO₂ 0.00 La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.75 0.73 0.75 0.75 0.75 Strain Pt (C.): 574 576 570 585 594 Anneal Pt (C.): 623 625 620 634 647 Softening Pt (C.): 880 879 869 887 905 CTE (×10{circumflex over ( )}−7/C.): 81.2 81.5 86 82.4 82.9 Density (g/cm{circumflex over ( )}3): 2.424 2.43 2.428 2.437 2.442 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) 1120 1120 1110 Hardness (MPa) −3.476 −3.27 −3.318 Liquidus temperature 9332.5 8742.7 8971.7 Fulcher_A 48.3 78.3 68 Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 76 77 78 79 80 SiO₂ 57.19 57.19 56.92 57.19 57.19 Al₂O₃ 15.22 15.22 15.15 15.22 15.22 P₂O₅ 7.56 7.56 7.53 7.56 7.56 B₂O₃ Li₂O Na₂O 15.50 15.50 15.43 15.50 15.50 K₂O 0.47 0.47 0.47 0.47 0.47 MgO 0.38 0.38 0.38 0.38 0.38 CaO 0.06 0.06 0.06 0.06 0.06 ZnO BaO TiO₂ 2.60 3.07 2.59 3.45 2.60 TeO₂ Nb₂O₅ SnO₂ 0.08 0.55 1.49 0.08 0.08 ZrO₂ 0.95 0.00 0.00 0.00 0.00 MnO₂ 0.00 0.00 0.00 0.09 0.95 La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.75 0.75 0.75 0.75 0.75 Strain Pt (C.): 586 593 576 572 Anneal Pt (C.): 636 643 625 622 Softening Pt (C.): 896 893 878 880 CTE (×10{circumflex over ( )}−7/C.): 82.8 81.3 82.1 82.8 Density (g/cm{circumflex over ( )}3): 2.441 2.465 2.432 2.436 Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 81 82 83 84 85 SiO₂ 63.46 61.47 60.48 63.46 61.47 Al₂O₃ 12.89 13.39 13.88 11.90 12.89 P₂O₅ 6.44 6.44 6.44 6.44 6.44 B₂O₃ Li₂O Na₂O 13.18 13.68 14.18 12.19 13.18 K₂O 0.00 0.00 0.00 0.00 0.00 MgO 0.00 0.00 0.00 0.00 1.98 CaO 0.05 0.05 0.05 0.05 0.06 ZnO 0.00 0.00 0.00 0.00 0.00 BaO TiO₂ 3.97 4.96 4.96 5.95 3.97 TeO₂ Nb₂O₅ SnO₂ ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.29 0.29 0.30 0.29 0.29 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 86 87 88 89 90 SiO₂ 61.48 60.47 60.47 60.49 60.49 Al₂O₃ 12.89 12.89 12.89 12.89 12.89 P₂O₅ 6.44 6.44 6.44 6.44 6.44 B₂O₃ Li₂O Na₂O 13.18 13.18 13.18 13.18 13.18 K₂O 0.00 0.00 0.00 0.00 0.00 MgO 0.00 2.98 1.99 1.00 0.00 CaO 0.05 0.06 0.06 0.05 0.05 ZnO 1.99 0.00 0.99 1.98 2.97 BaO TiO₂ 3.97 3.96 3.97 3.96 3.97 TeO₂ Nb₂O₅ SnO₂ ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.29 0.29 0.29 0.29 0.29 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 91 92 93 94 95 SiO₂ 59.47 59.48 59.48 59.50 59.49 Al₂O₃ 12.89 12.89 12.89 12.89 12.89 P₂O₅ 6.44 6.44 6.44 6.45 6.44 B₂O₃ Li₂O Na₂O 13.19 13.18 13.19 13.18 13.18 K₂O 0.00 0.00 0.00 0.00 0.00 MgO 3.96 2.98 1.98 0.99 0.00 CaO 0.08 0.06 0.06 0.05 0.05 ZnO 0.00 0.99 1.99 2.97 3.97 BaO TiO₂ 3.97 3.97 3.97 3.97 3.97 TeO₂ Nb₂O₅ SnO₂ ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.30 0.29 0.30 0.29 0.29 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 96 97 98 99 100 SiO₂ 58.28 58.28 58.28 58.28 58.28 Al₂O₃ 13.95 13.95 13.95 13.95 13.95 P₂O₅ 6.47 6.47 6.47 6.47 6.47 B₂O₃ Li₂O Na₂O 14.24 14.24 14.24 14.24 14.24 K₂O 0.00 0.00 0.00 0.00 0.00 MgO 1.00 1.00 1.00 0.99 1.00 CaO 0.05 0.05 0.05 0.05 0.05 ZnO 1.00 1.00 0.99 0.99 1.00 BaO TiO₂ 4.48 3.99 2.99 4.49 3.99 TeO₂ 0.00 0.00 0.00 0.50 1.00 Nb₂O₅ 0.50 1.00 1.99 0.00 0.00 SnO₂ ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.29 0.29 0.29 0.29 0.29 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 101 102 103 104 105 SiO₂ 58.27 57.87 57.73 57.59 56.78 Al₂O₃ 13.94 15.31 15.27 15.23 15.02 P₂O₅ 6.47 7.65 7.64 7.62 7.51 B₂O₃ Li₂O Na₂O 14.25 15.78 15.74 15.71 15.48 K₂O 0.00 0.48 0.48 0.48 0.47 MgO 0.99 0.38 0.38 0.38 0.38 CaO 0.05 0.05 0.05 0.05 0.05 ZnO 1.00 BaO TiO₂ 2.99 2.40 2.63 2.86 4.23 TeO₂ 2.00 Nb₂O₅ 0.00 SnO₂ 0.08 0.08 0.08 0.07 ZrO₂ MnO₂ La₂O₃ F— CeO₂ [R₂O—Al₂O₃] 0.31 0.95 0.95 0.96 0.93 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 106 107 108 109 110 SiO₂ 56.53 56.00 61.17 61.15 60.98 Al₂O₃ 14.95 14.81 13.55 13.17 12.56 P₂O₅ 7.47 7.41 6.29 6.11 5.83 B₂O₃ Li₂O Na₂O 15.41 15.27 14.04 13.93 13.90 K₂O 0.47 0.46 0.10 0.24 0.45 MgO 0.37 0.37 0.00 0.00 0.00 CaO 0.05 0.05 0.30 0.70 1.34 ZnO 0.00 0.00 0.00 BaO 0.00 0.00 0.00 TiO₂ 4.67 5.56 4.36 4.24 4.04 TeO₂ Nb₂O₅ SnO₂ 0.07 0.07 ZrO₂ MnO₂ La₂O₃ F— 0.19 0.45 0.90 CeO₂ [R₂O—Al₂O₃] 0.93 0.92 0.59 1.00 1.79 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 111 112 113 114 115 SiO₂ 58.89 58.92 58.94 58.89 58.92 Al₂O₃ 14.44 14.05 13.68 14.44 14.06 P₂O₅ 6.52 6.35 6.18 6.53 6.34 B₂O₃ Li₂O Na₂O 13.51 13.41 13.33 13.51 13.41 K₂O 0.09 0.23 0.36 0.09 0.22 MgO 1.86 1.81 1.77 0.00 0.00 CaO 0.28 0.68 1.06 0.29 0.68 ZnO 0.00 0.00 0.00 1.86 1.82 BaO 0.00 0.00 0.00 0.00 0.00 TiO₂ 4.20 4.08 3.97 4.20 4.08 TeO₂ Nb₂O₅ SnO₂ ZrO₂ MnO₂ La₂O₃ F— 0.19 0.45 0.71 0.19 0.46 CeO₂ [R₂O—Al₂O₃] −0.84 −0.41 0.01 −0.84 −0.43 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0 Example = 

Oxide [mole %] 116 SiO₂ 58.96 Al₂O₃ 13.68 P₂O₅ 6.18 B₂O₃ Li₂O Na₂O 13.33 K₂O 0.35 MgO 0.00 CaO 1.05 ZnO 1.76 BaO 0.00 TiO₂ 3.97 TeO₂ Nb₂O₅ SnO₂ ZrO₂ MnO₂ La₂O₃ F— 0.72 CeO₂ [R₂O—Al₂O₃] 0.00 Strain Pt (C.): Anneal Pt (C.): Softening Pt (C.): CTE (×10{circumflex over ( )}−7/C.): Density (g/cm{circumflex over ( )}3): Poisson's Ratio: Shear Modulus (Mpsi): Young's Modulus (Mpsi): Refractive Index: Stress optic coefficient Fracture toughness (MPa/m1/2) Hardness (MPa) Liquidus temperature Fulcher_A Fulcher_B Fulcher_T0

Example A: A patty each of the precursor glasses of Examples 3, 4, 5 and 44 was thermally treated as described above to form glass-ceramics. The glass-ceramics were then each ion exchanged in a bath including KNO₃, at a temperature of about 410° C. for a period of time until the DOL is about 50 μm. The CS and DOL measurements of each of these glass-ceramics are provided in Table II, according to methods otherwise described herein. For the glass-ceramics formed from the precursor glasses of Examples 3-5, SOC and RI of the glass precursors were utilized to determine CS and DOL of the glass-ceramic. For the glass-ceramic formed from the precursor glass of Example 44, testing was performed at 1550 nm wavelength and SOC and RI are assumed as 31.8 and 1.5, respectively.

TABLE II CS and DOL data for glass-ceramics formed from the precursor glasses of Examples 3, 4, 5 and 44. Example = 

Glass- Glass- Glass- Glass- ceramic ceramic ceramic ceramic based on based on based on based on Example 3 Example 4 Example 5 Example 44 CS (MPa) 1092.0 1093.1 1097.1 702 DOL (μm) 29.1 23.6 24.8 35 IX time (h) 2 2 2 1 CS (MPa) 1084.3 1080.0 1084.6 701 DOL (μm) 42.2 33.1 39.8 37 IX time (h) 4 4 4 2 CS (MPa) 1050.2 1052.3 700 DOL (μm) 47.5 57 42 IX time (h) 8 8 8 4

As shown in Table II, the glass-ceramic formed from the precursor glass of Example 44 achieved about the same DOL as the glass-ceramics based on Examples 3, 4, and 5, in half the time.

Example B: The glass-ceramics formed from the precursor glasses of Examples 3-5 were heat treated at close to softening point for about 20 hours. An XRD analysis was performed on the resulting glass-ceramics and an XRD pattern showing the results is shown in FIG. 2. The XRD pattern indicates that the glass-ceramics formed from the precursor glasses of Examples 3-5 have a predominant crystalline phase of rutile. FIGS. 3-5 show the SEM micrograph of the glass-ceramics formed from the precursor glasses of Examples 3, 4, and 5, respectively. The glass-ceramics were exposed to a 0.5% HF etchant for 30 seconds prior to being evaluated under the SEM and the SEM micrograph was taken at a magnitude of 25 kx with 60 degree tilt. The “needle-like” structures indicating a rutile crystalline phase are visible in FIGS. 3-5. The needle-like structures are enriched in titanium.

The glass-ceramic formed from the precursor glass of Example 44 was heat treated at 750° C. for 2 hours and then heat treated at 875° C. for 4 hours. The temperature was increased from 750° C. to 875° C. at a rate of about 5° C./minute. XRD analysis was performed on the resulting glass-ceramics; FIG. 6 shows the XRD pattern of the results. The XRD pattern indicates that the glass-ceramic formed from the precursor glass of Example 44 has a predominant crystalline phase of anatase. A SEM micrograph of the glass-ceramic formed from the precursor glass of Example 44 is shown in FIG. 7. The glass-ceramics were exposed to a 0.5% HF etchant for 30 seconds prior to being evaluated under the SEM and the SEM micrograph was taken at a magnitude of 25 kx with 60 degree tilt. The “needle-like” and bright structures indicating an anatase crystalline phase are visible in FIG. 6. The needle-like and bright structures are enriched in titanium.

Example C: The glass-ceramics formed from the precursor glasses of Examples 63-68 were heat treated at 825° C. for 2 hours and then heat treated at 1000° C. for 4 hours. The temperature was increased from 825° C. to 1000° C. at a rate of about 5° C./minute. XRD analysis was performed on the resulting glass-ceramics; FIG. 8 shows the XRD pattern of the results. The XRD pattern indicates that the glass-ceramic formed from the precursor glass of Example 63 has a predominant crystalline phase of anatase and the glass-ceramics formed from the precursor glasses of Examples 64-68 have a predominant crystalline phase of rutile.

FIG. 9 shows a transmission spectrum of a glass-ceramic article formed from the precursor glass of Example 63, having a thickness of 1.0 mm after being heat treated at 750° C. for 2 hours followed by heat treatment at 875° C. for 4 hours. FIG. 9 also shows a transmission spectrum of glass-ceramic articles formed from the precursor glasses of Examples 65-68, having a thickness of 1.0 mm after being heat treated at 850° C. for 2 hours followed by heat treatment at 925° C. for 4 hours.

FIG. 10 shows a transmission spectrum of glass-ceramic articles formed from the precursor glass of Example 94, each having a thickness of 0.8 mm. Each of the glass-ceramic articles were formed by heat treating a glass article having a composition according to Example 94 as follows: 1) heat treatment at 750° C. for 2 hours, followed by heat treatment at 900° C. for 4 hours; 2) heat treatment at 800° C. for 2 hours, followed by heat treatment at 875° C. for 4 hours; 3) heat treatment at 800° C. for 2 hours, followed by heat treatment at 900° C. for 4 hours; and 4) heat treatment at 800° C. for 2 hours, followed by heat treatment at 925° C. for 4 hours.

FIG. 11 shows a graph illustrating liquidus temperature and liquidus viscosity as a function of TiO₂ content, based on the Examples shown in Table I. The liquidus temperatures were measured by using the gradient boat method. Crushed glass was loaded into a platinum boat and held for 24 hours. The glass was then examined with an optical microscope and the highest temperature where crystals were observed was identified as the liquidus. The viscosity was measured as a function of temperature by the rotating cylinder method. This data was then used to calculate the viscosity at the liquidus temperature (liquidus viscosity). As shown in FIG. 11, liquidus viscosity decreases generally as TiO₂ content increases and liquidus temperature increases generally as TiO₂ content increases.

FIG. 12 shows a graph illustrating the variation in CIELAB color coordinates as a function of the compositional relationship (R₂O—Al₂O₃), based on Examples shown in Table I. The graph shows that L* hits a maximum of 97 at, when R₂O—Al₂O₃=0.8. When the value of (R₂O—Al₂O₃) increases, b* starts to increase. Opacity for all samples was between 98% and 99% for 0.8 mm thick samples.

The grain sizes of the crystals in the glass-ceramics according to one or more embodiments can be evaluated by scanning electron microscope images of the glass-ceramics. For example, as shown in FIGS. 3-5, some of the rutile crystals shown have a length of about 1 μm or less, 400 nm or less or 200 nm or less. As also shown in FIGS. 3-5, some of the rutile crystals shown have a width of about 50 nm or less.

Example D: The color of glass-ceramic articles according to the Examples shown in Table I was analyzed. The color measured is presented in CIELAB color space coordinates, as shown in Table III, and was determined from specular reflectance measurements using a spectrophotometer, with illuminant D65.

TABLE III Heat treatment conditions and SCI color measurements. Example = 

1 2 3 4 5 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 850 850 (Tc) (C.) Color L* 92.1 84.01 Color a* −0.11 0.07 Color b* 3.31 8.29 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 875 875 (Tc) (C.) Color L* 93.87 83.35 Color a* −0.45 −0.09 Color b* 1.46 0.68 Example = 

6 7 8 9 10 Heat treatment 1 700 700 700 700 (Tn) (C.) Heat treatment 2 750 825 750 750 (Tc) (C.) Color L* 94.28 92.62 91.4 92.34 Color a* −0.43 −0.03 −0.48 −0.19 Example = 

6 7 8 9 10 Color b* 6.42 2.49 9.72 10.52 Heat treatment 1 700 700 700 700 (Tn) (C.) Heat treatment 2 800 800 800 800 (Tc) (C.) Color L* 89.68 88.28 90.69 88.71 Color a* −1.6 0.73 −0.68 −0.06 Color b* 15.81 6.1 13.46 11.49 Heat treatment 1 700 700 700 700 (Tn) (C.) Heat treatment 2 825 850 850 850 (Tc) (C.) Color L* 90.82 94.12 82.91 93.74 Color a* 0.02 −0.24 1.26 −0.1 Color b* 13.41 2.68 12.03 2.36 Example = 

11 12 13 14 15 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 750 750 750 750 800 (Tc) (C.) Color L* 93.53 87.1 92.44 90.84 93.82 Color a* −0.27 0.11 −0.16 −0.07 −0.22 Color b* 7.99 11.07 11.29 12.72 7.38 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 800 800 800 800 850 (Tc) (C.) Color L* 90.37 91.51 88.87 88.12 93.12 Color a* 0.82 −0.05 0.05 0.82 −0.94 Color b* 8.97 1.39 11.62 10.65 2.08 Heat treatment 1 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 850 (Tc) (C.) Color L* 92.3 94.96 93.69 91.75 Color a* 0.97 −0.34 −0.25 1.22 Color b* 7.23 1.46 2.41 5.48 Example = 

16 17 18 19 20 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 800 800 800 800 800 (Tc) (C.) Color L* 92.46 95.14 89.68 87.3 90.93 Color a* 0.48 −0.59 0.12 0.58 0.23 Color b* 3.49 3.12 1.37 16.07 0.76 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 850 850 (Tc) (C.) Color L* 92.35 94.97 94.12 79.89 93.37 Color a* −0.71 −0.58 0.39 0.44 0.02 Color b* 2.08 3.7 1.93 −3.84 2.27 Example = 

21 22 23 24 25 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 825 825 825 825 825 (Tc) (C.) Color L* 89.89 92.83 88.18 93.01 87.94 Color a* −0.42 0.37 0.71 0.3 0.32 Color b* 7.63 1.72 16.67 1.66 13.15 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 800 800 800 800 800 (Tc) (C.) Color L* 88.54 89.08 92.22 88.55 88.16 Color a* 0.13 0.21 −0.19 −0.04 0.8 Color b* 8.57 1.57 12.27 0.74 14.34 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 850 850 (Tc) (C.) Color L* 93 93.72 84.68 93.54 85.57 Color a* −0.74 0.51 1.41 0.37 0.52 Color b* 9.93 1.82 8.14 1.68 11.41 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 91.98 93.98 87.26 95.1 87.7 Color a* −0.48 0.5 −0.36 0.14 0.78 Color b* 11.01 2.61 −2.91 1.54 2.98 Example = 

26 27 28 29 30 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 825 825 825 825 825 (Tc) (C.) Color L* 89.65 93.99 93.57 91.38 92.18 Color a* 1.03 −0.39 −0.14 0.77 −0.44 Color b* 4.35 0.61 0.93 3.07 0.68 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 800 850 850 850 850 (Tc) (C.) Color L* 89.23 95.01 94.42 91.86 94.96 Color a* 0.97 −0.38 −0.15 0.75 −0.55 Color b* 4.13 1.26 1.43 3.65 0.88 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 875 875 875 875 (Tc) (C.) Color L* 88.9 95.45 94.66 91.61 96.6 Color a* 1.01 −0.39 −0.17 0.56 −0.16 Color b* 3.94 1.33 1.39 2.42 1.44 Heat treatment 1 700 (Tn) (C.) Heat treatment 2 875 (Tc) (C.) Color L* 90.08 Color a* 0.3 Color b* 1.6 Example = 

31 32 33 34 35 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 825 825 850 850 850 (Tc) (C.) Color L* 91.92 91.71 96.11 95.83 95.52 Color a* −0.02 0.46 −0.39 −0.42 −0.3 Color b* 0.47 1.44 1.2 1.02 0.74 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 875 875 875 (Tc) (C.) Color L* 94.72 93.96 96.86 96.64 96.33 Color a* 0.2 0.66 −0.1 −0.1 −0.05 Color b* 0.82 1.84 1.8 1.83 1.38 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 95.51 94.19 96.95 96.86 96.92 Color a* 0.17 0.69 −0.17 −0.17 −0.18 Color b* 1.11 1.82 2.03 1.92 1.85 Heat treatment 1 — — — (Tn) (C.) Heat treatment 2 875 875 875 (Tc) (C.) Color L* 96.7 96.93 Example = 

31 32 33 34 35 Color a* −0.23 −0.14 Color b* 2.19 1.97 Heat treatment 1 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 (Tc) (C.) Color L* 94.07 94.04 93.72 Color a* −0.98 −0.9 −0.99 Color b* 0.5 0.02 −0.12 Heat treatment 1 — — — (Tn) (C.) Heat treatment 2 875 875 875 (Tc) (C.) Color L* 96.92 96.87 96.91 Color a* −0.17 −0.2 −0.21 Color b* 2.05 1.9 1.87 Heat treatment 1 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 (Tc) (C.) Color L* 95.97 95.86 95.46 Color a* −0.44 −0.42 −0.37 Color b* 1.23 1.01 0.73 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 875 875 (Tc) (C.) Color L* 96.65 96.34 Color a* −0.14 −0.09 Color b* 1.85 1.39 Example = 

36 37 38 39 40 Heat treatment 1 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 (Tc) (C.) Color L* 87.9 94.35 92.12 Color a* 0.97 0.24 0.15 Color b* 13.66 0.79 9.98 Heat treatment 1 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 (Tc) (C.) Color L* 86.85 95.21 91.95 Color a* 0.51 0.35 0.24 Color b* 10.17 1.47 11.26 Heat treatment 1 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 (Tc) (C.) Color L* 85.95 96.44 92.94 Color a* 0.82 −0.13 0.09 Color b* 10.09 1.42 9.81 Heat treatment 1 — — — (Tn) (C.) Heat treatment 2 875 875 875 (Tc) (C.) Color L* 73.79 96.67 93.1 Color a* 1.06 −0.04 −0.22 Color b* −2.68 1.77 8.6 Heat treatment 1 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 (Tc) (C.) Color L* 74.01 93.9 Color a* 8 −0.59 Color b* 18.03 0 Example = 

41 42 43 44 45 Heat treatment 1 700 700 700 750 (Tn) (C.) Heat treatment 2 850 850 850 875 (Tc) (C.) Color L* 87.9 94.35 92.12 93.76 Color a* 0.97 0.24 0.15 0.23 Color b* 13.66 0.79 9.98 1.36 Heat treatment 1 700 700 700 750 (Tn) (C.) Heat treatment 2 875 875 875 865 (Tc) (C.) Color L* 86.85 95.21 91.95 94.84 Color a* 0.51 0.35 0.24 0.29 Color b* 10.17 1.47 11.26 1.02 Heat treatment step 1 700 700 700 800/30 m Heat treatment step 2 875 875 875 925/2 h Color L* 85.95 96.44 92.94 94.37 Color a* 0.82 −0.13 0.09 −0.02 Color b* 10.09 1.42 9.81 1.26 Example = 

51 52 53 54 55 Heat treatment 1 0 0 0 0 0 (Tn) (C.) Heat treatment 2 900 900 900 900 900 (Tc) (C.) Color L* 95.81 96.05 96.03 94.38 Color a* −0.49 −0.48 −0.44 −0.63 Color b* 5.56 4.41 3.61 3.99 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 900 900 900 900 900 (Tc) (C.) Color L* 95.15 96.55 96.81 94.92 Color a* −0.76 −0.32 −0.22 −0.59 Color b* 6.71 3.98 3.25 4.46 Heat treatment 1 0 0 0 0 0 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 95.01 94.42 95.45 93.65 93.88 Color a* −0.83 −0.6 −0.53 −0.65 −0.05 Color b* 5.75 3.26 2.52 2.53 6.7 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 94.96 94.85 96.06 94.4 94.34 Color a* −0.83 −0.62 −0.44 −0.59 −0.36 Color b* 6.03 3.26 2.28 2.66 6.71 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 850 850 (Tc) (C.) Color L* 94.74 94.18 95.43 94.07 93.53 Color a* −0.83 −0.65 −0.52 −0.7 0.09 Color b* 5.84 2.9 2.17 2.21 7.66 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 825 825 825 825 825 (Tc) (C.) Color L* 94.17 93.15 92.78 91.01 91.34 Color a* −0.49 −0.84 −0.86 −0.95 0.91 Color b* 6.01 3.26 1.23 2.49 8.43 Example = 

56 57 58 59 60 Heat treatment 1 0 0 0 0 0 (Tn) (C.) Heat treatment 2 900 900 900 900 900 (Tc) (C.) Color L* 94.8 94.12 94.72 95.27 95.14 Color a* −0.69 −1.34 −0.63 −0.73 −0.49 Color b* 6.29 10.5 8.01 7.27 4.54 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 900 900 900 900 900 (Tc) (C.) Color L* 92.91 94.4 94.31 95.41 95.73 Color a* −0.05 −1.24 −0.75 −0.61 −0.42 Color b* 9.24 9.93 9.76 6.56 4.75 Heat treatment 1 0 0 0 0 0 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 90.35 93.53 93.72 94.83 94.45 Color a* 1.37 −1.22 −0.32 −0.53 −0.49 Color b* 9.69 8.5 9.87 7.7 3.99 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 90.92 94.55 95.29 95.21 94.43 Color a* 0.93 −0.36 −0.38 −0.31 −0.52 Color b* 8.98 8.48 6.77 6.62 3.89 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 850 850 (Tc) (C.) Color L* 89.9 93.1 94.21 94.4 93.57 Color a* 1.44 −1.27 −0.66 −0.22 −0.69 Color b* 10.89 7.01 9.07 8.26 3.93 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 825 825 825 825 825 (Tc) (C.) Color L* 87.39 91.2 92.98 93.45 91.71 Color a* 1.3 −1.7 −0.36 −0.04 −0.63 Color b* 12.88 5.03 8.47 7.29 3.77 Example = 

61 62 63 64 65 Heat treatment 1 0 0 750 850 (Tn) (C.) Heat treatment 2 900 900 875 925 (Tc) (C.) Color L* 95.36 92.95 94.83 91.79 Color a* −0.49 −0.15 0.09 −1.02 Color b* 6.63 1.93 0.91 −1.88 Heat treatment 1 700 700 775 (Tn) (C.) Heat treatment 2 900 900 875 (Tc) (C.) Color L* 95.5 93.58 95.18 Color a* −0.59 −0.03 0.13 Color b* 5.95 2.43 0.86 Heat treatment 1 0 0 800 (Tn) (C.) Heat treatment 2 875 875 900 (Tc) (C.) Color L* 94.82 92.85 95.32 Color a* −0.33 0.33 0.11 Color b* 7.4 2.46 1.2 Heat treatment 1 700 700 825 (Tn) (C.) Heat treatment 2 875 875 900 (Tc) (C.) Color L* 94.68 90.99 95.25 Color a* −0.13 1.03 0.14 Color b* 7.75 3.29 1.2 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 850 850 (Tc) (C.) Color L* 94.54 90.35 Color a* −0.49 1.12 Color b* 7.71 6.53 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 825 825 (Tc) (C.) Color L* 93.08 89.85 Color a* 0.08 0.04 Color b* 7.6 9 Example = 

66 67 68 69 70 Heat treatment 1 850 850 850 750 750 (Tn) (C.) Heat treatment 2 925 925 925 875 875 (Tc) (C.) Color L* 91.49 90.44 92.24 95.53 95.27 Color a* −1 −1.49 −1 −0.42 −0.46 Color b* −1.48 −2.97 −1.16 3.87 4.66 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 875 875 (Tc) (C.) Color L* 94.72 95.14 Color a* −0.53 −0.48 Color b* 3.35 4.07 Heat treatment 1 700 700 (Tn) (C.) Heat treatment 2 850 850 (Tc) (C.) Color L* 94.4 94.63 Color a* −0.54 −0.41 Color b* 3.57 5.02 Heat treatment 1 0 0 (Tn) (C.) Heat treatment 2 875 875 (Tc) (C.) Color L* 95 94.71 Color a* −0.45 −0.47 Color b* 3.31 4.06 Example = 

71 72 73 74 75 Heat treatment 1 750 750 750 750 750 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 94.42 95.22 95 95.18 94.01 Color a* −0.44 −0.25 −0.22 −0.26 −0.35 Color b* 5.68 5.31 4.96 4.43 7.47 Heat treatment 1 700 700 700 700 750 (Tn) (C.) Heat treatment 2 875 875 875 875 850 (Tc) (C.) Color L* 94.93 95.42 94.14 94.74 92.19 Color a* −0.52 −0.3 −0.35 −0.22 −0.5 Color b* 4.99 5.04 4.4 4.71 8.17 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 850 850 850 850 875 (Tc) (C.) Color L* 94.6 94.47 93.89 93.91 94.98 Color a* −0.28 −0.23 −0.46 −0.24 −0.11 Color b* 5.52 6.22 5.53 5.93 5.09 Heat treatment 1 0 0 0 0 0 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 95.21 95.22 94.02 94.87 95.38 Color a* −0.54 −0.29 −0.37 −0.32 −0.39 Color b* 5.21 5.14 3.84 4.36 4.38 Example = 

76 77 78 79 80 Heat treatment 1 750 750 750 750 750 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 94.31 93.69 95.27 Color a* −0.13 −0.3 −0.46 Color b* 6.39 4.61 4.66 Heat treatment 1 750 750 750 750 700 (Tn) (C.) Heat treatment 2 850 850 850 850 875 (Tc) (C.) Color L* 94.14 93.11 95.14 Color a* −0.29 −0.36 −0.48 Color b* 6.36 5.61 4.07 Heat treatment 1 700 700 700 700 700 (Tn) (C.) Heat treatment 2 875 875 875 875 850 (Tc) (C.) Color L* 93.61 93.45 94.63 Color a* −0.02 −0.29 −0.41 Color b* 7.57 4.41 5.02 Heat treatment 1 0 0 0 0 0 (Tn) (C.) Heat treatment 2 875 875 875 875 875 (Tc) (C.) Color L* 94.25 93.73 94.71 Color a* 0.05 −0.35 −0.47 Color b* 5.89 4.35 4.06 Example = 

86 87 88 89 90 Heat treatment 1 750 750 750 750 (Tn) (C.) Heat treatment 2 900 900 900 900 (Tc) (C.) Color L* 94.85 94.48 92.17 92.19 Color a* −0.49 −0.65 −1.01 −1.14 Color b* 0.99 0.46 −1.45 −1.43 Heat treatment 1 750 800 750 800 (Tn) (C.) Heat treatment 2 900 900 900 875 (Tc) (C.) Color L* 94.87 94.29 92.19 89.72 Color a* −0.48 −0.6 −1.08 −1.57 Color b* 1.08 0.58 −1.42 −3.06 Heat treatment 1 800 800 800 (Tn) (C.) Heat treatment 2 900 875 900 (Tc) (C.) Color L* 94.33 90.62 92.85 Color a* −0.55 −1.26 −1.09 Color b* 0.28 −2.51 −0.89 Heat treatment 1 800 800 825 (Tn) (C.) Heat treatment 2 900 875 900 (Tc) (C.) Color L* 94.34 90.58 93.14 Color a* −0.55 −1.27 −1 Color b* 0.33 −2.52 −0.56 Example = 

86 87 88 89 90 Heat treatment 1 825 800 (Tn) (C.) Heat treatment 2 900 900 (Tc) (C.) Color L* 94.12 92.77 Color a* −0.6 −0.96 Color b* −0.02 −0.92 Heat treatment 1 825 800 (Tn) (C.) Heat treatment 2 900 900 (Tc) (C.) Color L* 94.12 92.7 Color a* −0.58 −0.97 Color b* −0.03 −1.02 Example = 

91 92 93 94 95 Heat treatment 1 750 800 750 825 (Tn) (C.) Heat treatment 2 900 875 900 900 (Tc) (C.) Color L* 94.46 93.48 94.1 93.41 Color a* −0.52 −0.83 −0.63 −0.75 Color b* 1.23 −0.03 0.68 −0.49 Heat treatment 1 800 800 825 (Tn) (C.) Heat treatment 2 900 900 900 (Tc) (C.) Color L* 94.46 94.76 94.13 Color a* −0.51 −0.59 −0.69 Color b* 1.26 0.91 1.99 Example = 

108 109 110 111 112 Heat treatment 1 800 800 800 800 800 (Tn) (C.) Heat treatment 2 950 950 950 950 950 (Tc) (C.) Color L* 93.49 92.33 94.35 94.22 94.85 Color a* −0.62 −0.7 −0.25 −0.79 −0.58 Color b* 0.36 0.41 4.88 −0.07 0.7 Example = 

113 114 115 116 Heat treatment 1 800 800 800 800 (Tn) (C.) Heat treatment 2 950 950 950 950 (Tc) (C.) Color L* 94.88 93.82 93.55 95.45 Color a* −0.54 −0.9 −0.57 −0.66 Color b* 1.5 −0.67 −0.38 1.94

Example E: The indentation crack initiation load for a glass-ceramic formed from the precursor glass composition of Example 44 was measured using a Vickers indenter. The glass-ceramic was formed according to the methods described herein and IX as provided below in Table IV, along with the indentation threshold results.

TABLE IV Table IV: Vickers indentation crack initiation load for a glass- ceramic including the glass of Example 44. Example = 

44 Ion exchange 1 hour at 2 hours at 4 hours at condition 410° C. 410° C. 410° C. Indentation threshold 10 15 25 (kgf)

Example F: Various optical properties of Examples 63 and 65-68 were measured, including total transmission, opacity, transmission color, reflectance color and refractive index. One glass-ceramic sample each was formed from each of the precursor glasses of Examples 63 and 65-68. The samples had length and width dimensions of 1 inch (i.e., each sample was 1 square inch). The thickness of each sample is provided below in Table V. Each of the samples were polished, had a flat surface and exhibited a white color.

TABLE V Thickness of Examples 63, 65-68 used for opacity measurements. Example = 

63 65 66 67 68 Thickness (mm) 0.73 0.73 0.99 1.03 1.03

Prior to measurement, the surfaces of each sample was given a drag wipe cleaning using a Texwipe TX-609 wiper dampened with HPLC grade reagent alcohol. The samples were then measured for 2500 nm-250 nm total transmittance and total reflectance using a Perkin-Elmer 950 #2 spectrophotometer with 150 mm diameter sphere detector. The following parameters were used:

Spectral Bandwidth—PMT—3.0 nm

PbS—Servo, Gain—18

Scan Speed—420 nm/min

Scan Step Size—2 nm

Signal Average Time—0.2 Seconds

Aperture—None

The total transmittance measurement was obtained by fixing each sample at the sphere entry port to provide collection of off-axis scattered light transmitted by the sample if any exists. The total reflectance was measured with both white and black backing for determination of opacity. % Opacity is calculated using the equation:

${\%\mspace{14mu}{Opacity}} = {\frac{\%\mspace{14mu} R\mspace{14mu}{black}\mspace{14mu}{back}}{\%\mspace{14mu} R\mspace{14mu}{White}\mspace{14mu}{back}} \times 100.}$ The total transmittance of Examples 63 and 65-68 is shown in FIG. 13. Opacity of Examples 63 and 65-68 is shown in FIG. 14. The average opacity of Examples 63 and 65-68 is shown below in Table VI.

TABLE VI Average % Opacity of Examples 63 and 65-68. Example = 

63 65 66 67 68 Average % Opacity 82.42 93.32 94.34 97.91 96.78 over the visible spectrum (380 nm-780 nm)

The index of refraction measurements were performed on the Metricon Model 2010 Prism Coupler at 633 nm. The Metricon 2010 prism coupler operated as a fully automated refractometer, in which the refractive index of bulk materials and/or films can be measured. Refractive indices of bulk materials (e.g., Examples 63, and 65-68) were measured by the Metricon 2010 Prism Coupler using the following principle. If a material with an index of n is coupled to a prism with an index n_(p), laser light directed onto the base of the prism will be totally reflected until the angle of incidence θ becomes less than the critical angle θ_(c) where: θ_(c)=arc sin(n/n _(p))

The θc is measured using a photodetector (see FIG. 1) since the intensity on the detector drops significantly as θ drops below the critical angle. Since np is known, n can be determined from the above equation.

The instrument parameters used for the index measurements are as follows:

Substrate Mode

Half step table interval

Prism: 200-P-1, code 1073.6

Coupling load: ˜3.5 lb.

3 repeat scans

Source: 1550 nm laser

The instrument(s) used are calibrated periodically according to ASTM recommended procedures using absolute physical standards, or standards traceable to the National Institute of Standards and Technology (NIST).

The transmittance color results, reflectance color results (with black backing) and refractive index results are provided in Tables VIIA, VIIB and VIIC.

TABLE VIIA Table VIIA: Transmittance color results of Examples 63 and 65-58. Example = 

63 Illuminant CIE A Tristimulus: X = 22.06 Y = 17.08 Z = 1.65 Chromaticity: x = 0.5409 y = 0.4187 z = 0.0404 CIE L* a* b*: L* = 48.36 a* = 14.26 b* = 38.86 Illuminant CIE F02 Tristimulus: X = 17.83 Y = 16.18 Z = 2.62 Chromaticity: x = 0.4868 y = 0.4418 z = 0.0714 a*CIE L* a* b*: L* = 47.21 a* = 5.99 b* = 41.64 Illuminant CIE D65 Tristimulus: X = 15.69 Y = 14.92 Z = 4.46 Chromaticity: x = 0.4474 y = 0.4254 z = 0.1272 CIE L* a* b*: L* = 45.53 a* = 9.34 b* = 36.81 Example = 

65 Illuminant CIE A Tristimulus: X = 9.57 Y = 6.97 Z = 0.38 Chromaticity: x = 0.5656 y = 0.4122 z = 0.0222 CIE L* a* b*: L* = 31.75 a* = 14.98 b* = 38.28 Illuminant CIE F02 Tristimulus: X = 7.35 Y = 6.41 Z = 0.52 Chromaticity: x = 0.5151 y = 0.4489 z = 0.0361 CIE L* a* b*: L* = 30.42 a* = 7.18 b* = 40.75 Illuminant CIE D65 Tristimulus: X = 6.53 Y = 5.82 Z = 0.94 Chromaticity: x = 0.4917 y = 0.4378 z = 0.0706 CIE L* a* b*: L* = 28.94 a* = 11.25 b* = 36.30 Example = 

66 Illuminant CIE A Tristimulus: X = 8.20 Y = 5.93 Z = 0.27 Chromaticity: x = 0.5693 y = 0.4117 z = 0.0189 CIE L* a* b*: L* = 29.24 a* = 14.73 b* = 38.36 Illuminant CIE F02 Tristimulus: X = 6.28 Y = 5.44 Z = 0.36 Chromaticity: x = 0.5198 y = 0.4503 z = 0.0299 CIE L* a* b*: L* = 27.96 a* = 7.20 b* = 39.99 Illuminant CIE D65 Tristimulus: X = 5.57 Y = 4.91 Z = 0.66 Chromaticity: x = 0.4999 y = 0.4405 z = 0.0596 CIE L* a* b*: L* = 26.48 a* = 11.31 b* = 36.01 Example = 

67 Illuminant CIE A Tristimulus: X = 3.06 Y = 2.05 Z = 0.05 Chromaticity: x = 0.5935 y = 0.3975 z = 0.0089 CIE L* a* b*: L* = 15.75 a* = 14.15 b* = 25.12 Illuminant CIE F02 Tristimulus: X = 2.20 Y = 1.80 Z = 0.05 Chromaticity: x = 0.5435 y = 0.4433 z = 0.0131 CIE L* a* b*: L* = 14.37 a* = 7.73 b* = 23.58 Illuminant CIE D65 Tristimulus: X = 2.00 Y = 1.60 Z = 0.10 Chromaticity: x = 0.5401 y = 0.4324 z = 0.0275 CIE L* a* b*: L* = 13.25 a* = 12.14 b* = 21.36 Example = 

68 Illuminant CIE A Tristimulus: X = 5.24 Y = 3.65 Z = 0.11 Chromaticity: x = 0.5819 y = 0.4054 z = 0.0127 CIE L* a* b*: L* = 22.48 a* = 14.76 b* = 33.71 Illuminant CIE F02 Tristimulus: X = 3.91 Y = 3.28 Z = 0.14 Chromaticity: x = 0.5329 y = 0.4480 z = 0.0191 CIE L* a* b*: L* = 21.15 a* = 7.75 b* = 33.28 Illuminant CIE D65 Tristimulus: X = 3.49 Y = 2.94 Z = 0.26 Chromaticity: x = 0.5220 y = 0.4385 z = 0.0395 CIE L* a* b*: L* = 19.78 a* = 12.15 b* = 30.28

For transmittance color, the wavelength range was 380 nm to 780 nm, the spectral interval was 2 nm. A illuminant CIE, F02 illuminant CIE, D65 illuminant and a 10-degree standard observer angle were utilized to obtain the tristimulus, chromaticity and CIE L*a*b*measurements.

TABLE VIIB Table VIIB: Reflectance color results of Examples 63 and 65-58. Example = 

63 Illuminant CIE A Tristimulus: X = 86.60 Y = 80.34 Z = 30.84 Chromaticity: x = 0.4379 y = 0.4062 z = 0.1559 CIE L* a* b*: L* = 91.84 a* = −4.72 b* = −5.43 Illuminant CIE F02 Tristimulus: X = 82.51 Y = 81.14 Z = 60.17 Chromaticity: x = 0.3687 y = 0.3625 z = 0.2688 CIE L* a* b*: L* = 92.19 a* = −2.32 b* = −4.98 Illuminant CIE D65 Tristimulus: X = 76.01 Y = 81.95 Z = 94.17 Chromaticity: x = 0.3015 y = 0.3250 z = 0.3735 CIE L* a* b*: L* = 92.55 a* = −3.40 b* = −4.29 Example = 

65 Illuminant CIE A Tristimulus: X = 87.74 Y = 80.67 Z = 30.23 Chromaticity: x = 0.4417 y = 0.4061 z = 0.1522 CIE L* a* b*: L* = 91.98 a* = −3.35 b* = −3.91 Illuminant CIE F02 Tristimulus: X = 82.85 Y = 81.18 Z = 58.82 Chromaticity: x = 0.3718 y = 0.3643 z = 0.2640 CIE L* a* b*: L* = 92.21 a* = −1.77 b* = −3.51 Illuminant CIE D65 Tristimulus: X = 76.27 Y = 81.84 Z = 92.03 Chromaticity: x = 0.3049 y = 0.3272 z = 0.3679 CIE L* a* b*: L* = 92.50 a* = −2.67 b* = −2.91 Example = 

66 Illuminant CIE A Tristimulus: X = 87.10 Y = 79.92 Z = 29.69 Chromaticity: x = 0.4428 y = 0.4063 z = 0.1509 CIE L* a* b*: L* = 91.65 a* = −3.03 b* = −3.35 Illuminant CIE F02 Tristimulus: X = 82.10 Y = 80.38 Z = 57.77 Chromaticity: x = 0.3728 y = 0.3650 z = 0.2623 CIE L* a* b*: L* = 91.86 a* = −1.64 b* = −2.97 Illuminant CIE D65 Tristimulus: X = 75.54 Y = 80.95 Z = 90.39 Chromaticity: x = 0.3060 y = 0.3279 z = 0.3661 CIE L* a* b*: L* = 92.11 a* = −2.45 b* = −2.46 Example = 

67 Illuminant CIE A Tristimulus: X = 85.03 Y = 78.15 Z = 29.39 Chromaticity: x = 0.4416 y = 0.4058 z = 0.1526 CIE L* a* b*: L* = 90.85 a* = −3.26 b* = −4.08 Illuminant CIE F02 Tristimulus: X = 80.28 Y = 78.64 Z = 57.26 Chromaticity: x = 0.3714 y = 0.3638 z = 0.2649 CIE L* a* b*: L* = 91.07 a* = −1.69 b* = −3.77 Illuminant CIE D65 Tristimulus: X = 73.96 Y = 79.29 Z = 89.54 Chromaticity: x = 0.3046 y = 0.3266 z = 0.3688 CIE L* a* b*: L* = 91.37 a* = −2.50 b* = −3.14 Example = 

68 Illuminant CIE A Tristimulus: X = 90.41 Y = 82.57 Z = 30.15 Chromaticity: x = 0.4451 y = 0.4065 z = 0.1484 CIE L* a* b*: L* = 92.83 a* = −2.33 b* = −2.29 Illuminant CIE F02 Tristimulus: X = 84.92 Y = 82.95 Z = 58.63 Chromaticity: x = 0.3749 y = 0.3662 z = 0.2589 CIE L* a* b*: L* = 92.99 a* = −1.30 b* = −1.95 Illuminant CIE D65 Tristimulus: X = 78.04 Y = 83.35 Z = 91.75 Chromaticity: x = 0.3083 y = 0.3293 z = 0.3624 CIE L* a* b*: L* = 93.17 a* = −1.96 b* = −1.57

For transmittance and reflectance color, the wavelength range was 380 nm to 780 nm, the spectral interval was 2 nm. CIE illuminants F02 and D65 and a 10-degree standard observer angle were utilized to obtain the tristimulus, chromaticity and CIE L*a*b*measurements.

TABLE VIIC Table VIIC: Refractive Index of Examples 63 and 65-58. Example = 

63 65 66 67 68 Refractive 1.4919 1.4970 1.4972 1.4992 1.4969 Index at 1550 nm

Examples 117-128: The exemplary precursor glass compositions listed in Table VIII were made in the same manner as Examples 1-116 and were formed into molten precursor glass that was then cast as patties of precursor glass in the same manner as Examples 1-116. The patties of precursor glass were then thermally treated to form glass-ceramics, as described above with respect to Examples 1-116. The resulting glass-ceramics were also analyzed for the properties listed in Table VIII, in the same manner as Examples 1-116.

TABLE VIII Table VIII: Precursor glass compositions. Example = 

117 118 119 120 121 Oxide [mole %] Al₂O₃ 13.88 13.88 13.84 13.84 13.85 B₂O₃ 0.00 0.00 0.00 0.00 0.00 CaO 0.04 0.05 0.04 0.04 1.00 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 K₂O 0.06 0.06 1.00 0.06 0.06 Li₂O 0.00 0.93 0.00 0.00 0.00 MgO 1.99 1.97 1.97 1.98 1.99 Na₂O 14.78 13.73 13.85 13.83 13.79 P₂O₅ 6.37 6.36 6.42 6.43 6.38 SiO₂ 59.96 60.11 59.99 60.00 60.05 SnO₂ 0.00 0.00 0.00 0.00 0.00 TiO₂ 2.90 2.90 2.88 2.88 2.88 ZnO 0.01 0.01 0.00 0.95 0.00 [R₂O—Al₂O₃] 0.96 0.84 1.01 0.05 0 Annealing temperature 650 650 650 650 650 (C.) Tn (C.) for 30 min 775 775 775 775 775 Tc (C.) for 2 hours 925 925 925 925 925 Softening 887.7 872.3 892.3 892 910.3 Annealing Pt. (C.) 621 606 620 620 636 Strain Pt. (C.) 574 562 573 574 590 Density (g/cm³) 2.427 2.427 2.427 2.437 2.429 CTE (×10⁻⁷/C) 79.2 78.6 81.7 75.8 76.6 liquidus air 1090 1080 1090 1080 1080 internal 1075 1080 1085 1075 1080 platinum 1070 1070 1080 1070 1070 primary crystalline phase rutile Rutile rutile Rutile rutile liquidus viscosity (72 h gradient boat) air 264467.8 235510.3 292648.2 318929.5 334228.9 internal 353452.7 235510.3 321990.9 351815.3 334228.9 platinum 389988.5 284787.1 354564.3 388414.3 407190.8 Indentation threshold HTV-A −4.221 −4.219 −4.313 −4.616 −4.474 HTV_B 11219.1 11244.5 11571.9 12064.7 11756.7 HTV-B0 −73.4 −92.4 −93.3 −112.2 −95.9 log(D(cm2/s)) heat treatment Color L* 95.87 95.35 96.17 94.59 95.11 Color a* −0.28 −0.26 −0.31 −0.65 −0.31 Example = 

117 118 119 120 121 Color b* 2.91 2.07 2.85 1.42 1.47 Example = 

122 123 124 125 126 Oxide [mole %] Al₂O₃ 13.94 14.19 14.13 14.14 14.21 B₂O₃ 0.5 4.17 4.44 4.35 4.15 CaO 0.04 0.05 0.05 0.05 0.05 Fe₂O₃ 0.01 0.01 0.01 0.01 0.01 K₂O 0.06 0.02 0.02 0.02 0.02 Li₂O 0 0 0 0 0 MgO 2.01 2.67 2.66 2.65 2.62 Na₂O 13.73 13.27 13.34 13.35 13.19 P₂O₅ 6.36 1 1.01 1 0.99 SiO₂ 60.45 62.1 61.33 60.91 60.77 SnO₂ 0 0.09 0.09 0.09 0.09 TiO₂ 2.91 2.44 2.91 3.42 3.9 ZnO 0 0 0 0 0 [R₂O—Al₂O₃] −0.15 −0.9 −0.77 −0.77 −1 Annealing temperature 650 650 650 650 650 (C.) Tn (C.) for 30 min 775 775 775 775 775 Tc (C.) for 2 hours 925 925 925 925 925 Softening 887.9 Annealing Pt. (C.) 614 Strain Pt. (C.) 5666 Density (g/cm³) 2.414 CTE (×10⁻⁷/C) 75.9 Liquidus air 1110 1100 1145 1145 1190 internal 1105 1100 1140 1140 1190 platinum 1090 1085 1125 1130 1170 primary crystalline phase rutile Rutile rutile rutile rutile liquidus viscosity (72 h gradient boat) air 178562.3 internal 195696.2 platinum 258767.8 Indentation threshold HTV-A −4.612 HTV_B 12274.5 HTV-B0 −134.4 Example = 

122 123 124 125 126 log(D(cm2/s)) heat treatment Color L* 95.06 92.15 Color a* −0.33 −0.76 Color b* 1.5 −2 Example = 

127 128 Oxide [mole %] Al₂O₃ 14.43 14.33 B₂O₃ 3.18 3.45 CaO 0.05 0.05 Fe₂O₃ 0.01 0.01 K₂O 0.02 0.02 Li₂O 0 0 MgO 2.66 2.68 Na₂O 13.31 13.46 P₂O₅ 1.51 1.55 SiO₂ 61.78 60.49 SnO₂ 0.09 0.09 TiO₂ 2.96 3.88 ZnO 0 0 [R₂O—Al₂O₃] −1.1 −0.85 Annealing temperature 650 650 (C.) Tn (C.) for 30 min 775 775 Tc (C.) for 2 hours 925 925 Softening Annealing Pt. (C.) Strain Pt. (C.) Density (g/cm³) CTE (×10⁻⁷/C) Liquidus air 1130 1180 internal 1120 1170 platinum 1120 1170 primary crystalline phase rutile rutile liquidus viscosity (72 h gradient boat) air internal platinum Indentation threshold Example = 

127 128 HTV-A HTV_B HTV-B0 log(D(cm2/s)) heat treatment Color L* 92.13 91.97 Color a* −0.72 −0.86 Color b* −1.81 −2.34

Comparative Example 129, Examples 130-134 and Comparative Example 135: The exemplary glass precursors listed in Table IX were made in the same manner as Examples 1-128 and were formed into molten precursor glass that was then cast as patties of precursor glass in the same manner as Examples 1-128. The patties of precursor glass of Examples 130-134 and Comparative Example 135 were then thermally treated to form glass-ceramics, as described above with respect to Examples 1-128. The resulting glass-ceramics were also analyzed for the properties listed in Table IX, in the same manner as Examples 1-128. Glasses formed from comparative Example 129 were not thermally treated to form glass-ceramics.

TABLE IX Precursor glass compositions. Comparative Comparative Composition (mol %) Ex. 129 Ex. 130 Ex. 131 Ex. 132 Ex. 133 SiO₂ 67.5 65.1 64.6 64.1 58.5 Al₂O₃ 12.7 12.7 12.7 12.7 12.7 B₂O₃ 3.7 3.9 3.9 3.9 9.7 Li₂O 0 0 0 0 0 Na₂O 13.6 13.8 13.8 13.8 13.6 MgO 2.4 2.4 2.4 2.4 2.4 ZnO 0 0 0 0 0 TiO₂ 0 2.0 2.5 3 3.0 SnO₂ 0.1 0.1 0.1 0.1 0.1 [R₂O—Al₂O₃] 0.9 1.1 1.1 1.1 0.9 Tn (C) N/A 775° C. for 2 775° C. for 2 775° C. for 2 775° C. for 2 hours hours hours hours Tc (C) N/A 920 for 4 920 for 4 920 for 4 920 for 4 hours hours hours hours Liquidus Temprature 1005 1000 1050 1090 1055 (° C.) Liquidus viscosity 2,210,000 1,620,000 500,000 185,000 51,800 (Poise) Comparative Comparative Composition (mol %) Ex. 129 Ex. 130 Ex. 131 Ex. 132 Ex. 133 IX - salt KNO₃ KNO₃ KNO₃ KNO₃ IX bath temperature (° C.) — 410 410 410 410 IX bath time (hr) — 16 16 16 16 Indentation threshold 10-15 20-25 10-15 10-15 9-10 (kgf) Compararive Composition (mol %) Ex. 134 Ex. 135 SiO₂ 58 69.2 Al₂O₃ 12.7 12.6 B₂O₃ 9.7 1.8 Li₂O 0 7.7 Na₂O 13.6 0.4 MgO 2.4 2.9 ZnO 0 1.7 TiO₂ 3.5 3.5 SnO₂ 0.1 0.2 [R₂O—Al₂O₃] 0.9 −4.5 Tn (C) 775° C. for 2 775° C. for 2 hours hours Tc (C) 920 for 4 920 for 4 hours hours Liquidus Temprature 1105 1245 (° C.) Liquidus viscosity 19,300 10,550 (Poise) IX - salt NaNO₃ IX bath temperature (° C.) 430 IX bath time (hr) 2 Indentation threshold 7-9 (kgf)

The liquidus temperature of Comparative Example 129, Examples 130-134 and Comparative Example 135 was determined by forming a glass powder from the precursor glasses and then isothermally holding the glass powder in a gradient furnace for 72 hours. The viscosity at liquidus temperature for each of Comparative Example 129, Examples 130-134 and Comparative Example 135 was determined from the measurement of high temperature viscosity. Indentation threshold values were determined on the glass formed from Comparative Example 129 (which was not thermally threated to a glass-ceramic) and the glass-ceramics of Examples 130-134 and Comparative Example 135. The glass-ceramics of Examples 130-134 and Comparative Example 135 were ion exchanged at the designated salt bath, at the times and temperatures listed in Table IX prior to testing with a Vickers indenter. The glass formed from Comparative Example 129 was formed using the same process as used to form the glass-ceramics of Examples 130-134 and Comparative Example 135 but was not ion exchanged and exhibited Vickers Indentation Crack Initiation load values in the range from about 10 kgf and 15 kgf For comparison, the precursor glass composition for Comparative Example 129 was formed into a glass article using a fusion draw process and the resulting glass article exhibited Vickers Indentation Crack Initiation load value of from about 20 kgf to about 25 kgf.

FIG. 15 shows x-ray diffraction spectra of the crystalline phases of the glass-ceramics formed from Examples 130-132, after ceramming at 920° C. for 4 hours. The spectra shows the presence of armalcolite in all three glass-ceramics. The remaining portions of the glass-ceramics remained amorphous.

FIGS. 16A and 16B show high angle annular dark field (HAADF) mapping images for the glass-ceramic of Example 131, after ceramming at 920° C. for 4 hours. FIGS. 17A-17D show energy-dispersive x-ray (EDX) mapping images for the glass-ceramic of Example 131, after ceramming at 920° C. for 4 hours, for elements Mg, Ti, Al and Si, respectively. Without being bound by theory, the glass-ceramic in FIGS. 16A-B and 17A-D may exhibit translucency or opacity depending on the size of the crystals in the crystalline phase or the amount of the formed armalcolite phase.

FIGS. 18A and 18B shows graphical representations of CIELAB color space coordinates L*, a* and b* for the glass-ceramics formed form Examples 130-132 and Comparative Example 135, as measured using a spectrophotometer (supplied by X-rite, model Color i7) with illuminant F02 and specular reflectance included. In FIGS. 18A and 18B, the square data points and diamond data points indicate color coordinates measured after ceramming at 920° C. for 4 hours and 940° C. for 4 hours, respectively.

FIG. 19 shows the concentration of K+ ions present in a glass-ceramic formed from Example 131 (after ceramming at 920° C. for 4 hours) as a function of depth, after being ion exchanged in a molten salt bath including KNO₃, having a temperature of 430° C., for two different time periods: 8 hours and 16 hours.

FIG. 20 shows the concentration of Na+ ions present in the glass-ceramic formed from Example 131 (after ceramming at 920° C. for 4 hours) as a function of depth, after being ion exchanged in a molten salt bath including NaNO₃, having a temperature of 430° C., for two different time periods: 8 hours and 16 hours.

Various modifications and variations can be made to the materials, methods, and articles described herein. Other aspects of the materials, methods, and articles described herein will be apparent from consideration of the specification and practice of the materials, methods, and articles disclosed herein. It is intended that the specification and examples be considered as exemplary. 

What is claimed is:
 1. A glass-ceramic article comprising: a predominant crystalline phase comprising anatase, rutile, or a combination thereof; and a composition, in mol %, comprising: SiO₂ in the range from about 45 to about 75; Al₂O₃ in the range from about 4 to about 25; P₂O₅ in the range from about 0.1 to about 10; MgO in the range from about 0 to about 4; R₂O in the range from about 0 to about 33; ZnO in the range from about 0 to about 5; ZrO₂ in the range from about 0 to about 4; TiO₂ in the range from about 0.5 to about 10; and B₂O₃ in the range from about 0 to 4.44, wherein R₂O comprises one or more of Na₂O, Li₂O and K₂O.
 2. The glass-ceramic article of claim 1, wherein (R₂O—Al₂O₃) is in the range from about −4 to about
 4. 3. The glass-ceramic article of claim 1, wherein the composition comprises, in mol %, Li₂O in the range from about 0 to about 12; Na₂O in the range from about 4 to about 20; and K₂O in the range from about 0 to about
 2. 4. The glass-ceramic article of claim 1, wherein the composition comprises, in mol %, B₂O₃ in the range from about 2 to 4.41.
 5. The glass-ceramic article of claim 1 further comprising a total crystalline phase of up to 20% by weight.
 6. The glass-ceramic article of claim 1, further comprising a compressive stress layer extending from a surface of the glass-ceramic article to a depth of the compressive stress layer, the compressive stress layer comprising a compressive stress of about 200 MPa or greater and the depth of compressive stress layer of about 15 μm or greater.
 7. The glass-ceramic article of claim 6, further exhibiting a Vickers indentation crack initiation load of about 10 kgf or greater.
 8. A glass-ceramic article comprising: a predominant crystalline phase comprising anatase, rutile, or a combination thereof, wherein the glass-ceramic article is formed from a precursor glass having a liquidus viscosity of about 20 kP or greater.
 9. The glass-ceramic article of claim 8, wherein the predominant crystalline phase comprises crystals having a length of about 1 μm or less and a width of about 50 nm or less.
 10. The glass-ceramic article of claim 8, wherein the combined amount of anatase and rutile is less than about 12 wt. %, of the glass-ceramic article.
 11. The glass-ceramic article of claim 8, further comprising a color presented in CIELAB color space coordinates determined from specular reflectance measurements selected from any one of: CIE a* in the range from about −2 to about 8, CIE b* in the range from about −7 to about 30, and CIE L* in the range from about 85 to about 100; and CIE a* in the range from about −1 to about 0, CIE b* in the range from about −7 to about −3, and CIE L* in the range from about 85 to about
 100. 12. The glass-ceramic article of claim 8, further exhibiting a Vickers indentation crack initiation load of about 10 kgf or greater.
 13. An electronic or portable computing device comprising the glass-ceramic article of claim
 1. 14. An electronic or portable computing device comprising the glass-ceramic article of claim
 8. 